WO2023147248A1 - Résine liante et son procédé de production - Google Patents

Résine liante et son procédé de production Download PDF

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Publication number
WO2023147248A1
WO2023147248A1 PCT/US2023/060901 US2023060901W WO2023147248A1 WO 2023147248 A1 WO2023147248 A1 WO 2023147248A1 US 2023060901 W US2023060901 W US 2023060901W WO 2023147248 A1 WO2023147248 A1 WO 2023147248A1
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WIPO (PCT)
Prior art keywords
resin
admixture
yield
laminate
eugenol
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PCT/US2023/060901
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English (en)
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James CARUTHERS
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Purdue Research Foundation
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Publication of WO2023147248A1 publication Critical patent/WO2023147248A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/08—Ureas; Thioureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/38—Block or graft polymers prepared by polycondensation of aldehydes or ketones onto macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ

Definitions

  • the present novel technology relates generally to chemistry and chemical engineering and, more particularly, improved resin binder systems and methods of manufacturing the same.
  • Binders are materials used to hold disparate materials together. Resin binders are widely used in construction for to hold together partition walls, restroom dividers, countertops, and the like. Resin binder systems nay be sorted into two grades, HPL (High Pressure Laminate, static press) and CPL (Continuous High-Pressure Laminate) differing in the method of manufacturing.
  • HPL High Pressure Laminate, static press
  • CPL Continuous High-Pressure Laminate
  • the current choice of binder system is a phenol-formaldehyde mixture in a 1.4 to 2.2 mole ratio of formaldehyde (F) to phenol (P). Both phenol and formaldehyde are chemicals where environmental concerns are going to require reduction in VOC by 50%.
  • the European Union is asking for a significant reduction for phenol and the California Air Research Board (CARB) is requiring these laminate materials to meet CAR.B2 limits with less than 0.7 ppm Formaldehyde in
  • the present novel technology relates to a process for depolymerizing lignin from a variety of forestry and agricultural waste sources such as wood fibers or rice straw.
  • the depolymerized lignin can be used as partial replacement for phenol, and the formaldehyde-free crosslinkers glyoxal and Polycup are used to reduce and/or eliminate the amount of formaldehyde used in an HPL and/or CPL (POLYCUP is a registered trademark of Solenis Technologies, L.P. LIMITED PARTNERSHIP DELAWARE 3 Beaver Valley Road, Suite 500 Wilmington DELAWARE 19803, registration no. 3427580).
  • the components of the novel binder system include:
  • the paper is made predominantly of southern pine and the porosity of the kraft paper is 10 to 20 seconds (porosity is measured by how long it takes lOOcc of air to travel though a 1-inch Gurley Porosity instrument).
  • This paper is saturated with 30+2% by weight of resin, where the resin includes 6% by weight of volatiles before being placed in the press.
  • Waxes are used to improve water tolerance properties. Two waxes were used: (i) an experimental wax from Astro American Chemical Company designated Emulsion 002 Paraffin and Slack Wax and (ii) Michelman Inc. 66035 High Density Polyethylene Wax.
  • urea and Polycup are added to the mixture with additional KOH and heated to 82°C for 10 minutes (second cook).
  • the second addition of KOH ensures more basic conditions which are desired for reaction with Polycup.
  • the new resin is added as an extender to the standard phenol formaldehyde laminating resin.
  • Resins were made consisting of between 50% to 75% of the traditional phenolformaldehyde with the remainder from the pre-cooked eugenol-based resin, although the resins could contain as little as 25% of the traditional phenol-formaldehyde with the remainder from the pre-cooked eugenol-based resin, or even 100% pre-cooked eugenol- based resin.
  • resins samples with 100% of the traditional phenolformaldehyde resin currently used in the laminate industry were also produced in order to establish a baseline to which to compare the novel extended resins.
  • Sheets of kraft paper were supplied as rolls of kraft of papers 5-foot wide and 6000 feet long. These were cut into more manageably sized sheets of 24-inch x 24-inch. These sheets were cut into (i) 4-inch by 4-inch squares or (ii) 4-inch by 8- inch strips that were eventually cut into 4-inch by 4-inch squares after B-Stage curing. Three-inch by eight-inch strips were also cut.
  • the impregnated paper was dried in oven at 138°C. The samples were removed from the oven at one-minute intervals and weighed. When the weight of the impregnated paper was between 13 to 14 g for a wet paper that initially weighed 20 g, the A-stage part of the cure was complete. This typically took 6 minutes. The mass of the paper increased by 28 to 30% at the end of the A-stage; specifically, a 10-gram sheet of dry kraft paper will weight 18 to 20-grams wet, which will decrease to between 13 to 14-grams prior to B-stage cure. At this point approximately 0.8 g of the sheet remain as volatiles (mainly as water and methanol but it also includes excess formaldehyde, phenol, furfural, and some diols).
  • Boiling Water Resistance (ISO 4586). Using a heat plate, water is brought to a rolling boil, where samples are then dropped into the water and kept below the surface for 30 minutes. The industry standard is 2 hours, where the Purdue testing thus far has only been for 30 minutes. The surface finish is then examined with ratings from no visible change to surface blistering to delamination of the layers. The laminate thickness is then measured, and the percent increase is the Thickness Swell. The laminate is then weighed, and the percentage increase is the Water
  • Blister Test via Radiant Heat Strip Element Method This test was performed to assess the effect of the radiant heat that is used to make a curved countertop surface. The test involved the use of 1600 watt two element radiant electric heater strips placed 10 cm (4-in) from the surface of the test specimen. The 7.5 cm by 20 cm (3-in by 8-in) samples were cut to 5 cm by 20 cm (2-in by 8-in) specimens and conditioned for 48 hours prior at immersion in an environment characterized by a temperature of 23°C and relative humidity of 50%. Calibration strips with thermochromic ink indicated when the temperature had reached 163°C (325°F), which indicates the beginning of the test.
  • the surface is observed as a function of time up to the point of blister or 120 seconds if no blister is observed, where damage such as discoloration, blistering, charring, crazing and/or deformation is observed via mirror at bottom of apparatus. The time at which any damage occurs was observed and recorded.
  • Post forming test for laminate requires a two-element heater and a radius forming apparatus. Place the laminate face down onto heating element apparatus. Then heat the laminate to the 163°C forming temperature. Allow forming apparatus to bend laminate into shape and record observations/damage. Failure is defined by the observation of fractures, blisters, and/or crazing. Ball Impact Resistance. Test for the core of the laminate to avoid damage from a falling 3.8 cm (1.5 in) diameter polished stainless-steel ball weighing 224 + 3 grams. The test specimen is 30.5 cm by 30.5 cm (12x12 in) laminate that is no less than 6 mm thick. The ball is dropped from ever increasing heights until visible damage such as fractures is observed, at which point the height is recorded. Dimensional Stability.
  • This test measures the changes in laminate shape for a wide range of temperatures and relative humidity in a humidity chamber.
  • the laminate size is at least 120 mm x 120 mm.
  • the midpoint is located between two adjacent corners and 10 mm from the edge and marked. Repeat for the other three sides of the sample. These marks will be used after the test if the sample warped or changes dimensions. Measure initial and final mark points. Two conditions are tested: (i) in an oven at 70°C for 24 hours and (ii) in a humidity chamber at 90% humidity at 40°C for seven days.
  • the next set of 7.5 cm by 20 cm (3 in x 8 in) laminate specimens were manufactured in the press to ensure more consistent and even pressure with approximately 588400 N (60-tons force) at 144°C for 11 minutes.
  • the composition is given in Table 6.
  • Two samples were 70/30 mixtures of CPL resin with rice eugenol resin.
  • the third sample was a 70/30 mixture of CPL resin with wood eugenol resin.
  • the manufacturing protocol for these specimens was: (i) B-Stage cure at 138°C followed by (ii) 588400 N (60 tons pressure) at 140°C for 24 minutes.
  • Two 15 cm by 20 cm (6”x8”) test specimens were produced using paper made of 50% Bagasse, which is the pulp residue after the extraction of sugar cane juice. Bagasse Sample 2 had more depolymerized rice lignin as shown in Table 6, thereby decreasing glyoxal to rice lignin ratio which decreases the extent of crosslinking.
  • the manufacturing history for Sample 1 was: (i) a B-stage cure at 138°C (ii) 588400 N (60 tons pressure) at 140°C for 24 minutes.
  • Sample 2 The manufacturing history for Sample 2 was: (i) a B-stage cure at 132°C followed by (ii) curing in a hot press with 60 tons of pressure at 140°C for 24 minutes.
  • the reason for the lower B-stage cure for Sample 2 was an observation made with Sample 1 is that the Bagasse specimens were curing faster than normal, where it was later realized that this is because the pH of the Bagasse material is higher which results in a faster cure.
  • Waxes were added to the resin mixture before brushing the resin onto the paper for the B-Stage cure. Waxes tested include (i) an experimental wax from Astro American Chemical Co. designated Emulsion 002 Paraffin and Slack Wax and (ii) Michelman Inc. 66035 High Density Polyethylene Wax. DOSS (dioctyl sulfosuccinate) was added into the resin as well to aid with penetration into the kraft paper. Michelman Wax was found to mix better with our resin mixture. The resin composition of the three laminates is given in Table 8.
  • each laminate sample consisted of two resin impregnated kraft paper sheets. Above these sheets, a decor paper was placed.
  • the decor print paper used was a typical decor print paper with wood print.
  • a clear overlay sheet made of melamine formaldehyde high flow resin mixed with aluminum oxide particles (size 220F) was placed as the top layer of each sample.
  • This overlay is a fast cure overlay and is used in the flooring industry.
  • the primary task of an overlay is as a protective wear layer with a secondary objective of stain resistance.
  • the laminates were manufactured using the standard industry method of stacking multiple laminates within the press. On the top and bottom of each laminate with overlay sheet was a thin sheet of aluminum foil coated with 7991 polyethylene with siloxane mold release.
  • Press pads were used to separate the laminates and the aluminum foil release layer, where the press pads are pieces of plain kraft paper wrapped in aluminum foil.
  • the detailed arrangement of the stack of materials in the press is given in Table 9.
  • the laminate assembly detailed in Table 9 was placed in a PHI press under 588400 N (60 tons) (corresponding to 833 psi for the 930 cm 2 (144 in 2 ) laminate assembly) for 24 mins at 140°C.
  • the manufacturing process did not function fully as intended, where the second hood kraft paper laminate that was sandwiched in the middle of the layup did not form a laminate.
  • the hood kraft paper laminate delaminated upon removal from the layup, which is likely due to heat transfer limitation to the center of the layup where this hood kraft paper laminate was located. Notwithstanding the difficulties with the centermost laminate material, we believe the thermal history of the outer laminates was able to cure the resin.
  • the laminates were tested for water absorption and thickness swell, where the results are shown in Table 10.
  • the added wax added substantially in the reduction of water absorption as compared to data in the previous sets of experiments.
  • the addition of wax had a minimal effect on thickness swell.
  • the values of 15% water adsorption and 15% thickness swell are well in line with industry standards.
  • Sample 1 of the Bagasse laminate delaminated which we ascribe to over-curing during the B-Stage process that was indicated by the color of the B-Stage kraft paper after the B-Stage cure process. Specifically, over-cured samples look lighter in color and have a golden sheen whereas properly B-Staged kraft paper still has a darker brown hue.
  • the next step is to produce larger, 5 -ply test specimens so that the specimens can be tested using the full suite of NEMA and ISO Standards in order to prove the commercial viability of this system.
  • a binder system (the glue that holds the composite together) for wood-based composite board products has been developed that uses depolymerized lignin as the major component in the binder system.
  • depolymerized lignin was used just as it comes out of the bioreactor, where both the clean cellulose and majority of the methanol solvent were removed which are easy separation process. However, the remaining reaction mass that contains lignin monomers, residual solvent and sugars was used as received, without any additional purification.
  • the lignin monomer feedstock was prepared by catalytic depolymerization of poplar wood chips. Specifically, 100 to 200 g of 70 mesh dried wood biomass was reacted under batch conditions with 10% by weight catalyst in 1-2 L methanol solvent under hydrogen pressure (30-50 bar) at 200- 225 °C for several hours. Solid filtration followed by solvent concentration under rotary evaporation provided the lignin methoxyphenols feedstock used in resin preparations.
  • the depolymerized lignin resin was used as received. Specifically, the cellulosic fraction of the wood chips had been removed (except for a limited number of tests) and greater than 95% of the methanol solvent was also removed. However, the remaining reaction mixture was not purified any further. This mixture contains propyl methoxyphenols (see structures above) as the main components, but also includes other minor reaction products including xylose as well as a residual methanol solvent.
  • binder technology described herein works with the unpurified reaction mixture after the relatively easy removal of the lignin free cellulose solid byproduct and most of the methanol solvent, thereby avoiding the need for costly separation processes.
  • the ability to avoid costly separation operations significantly affects the overall economics of the lignin monomer binder system.
  • Polycup 9700 curing agent Polycup is a commercial crosslinking resin sold by Solenis and originally developed by Ashland Chemical. Polycup is a water soluable polyamide-epichlorohydrin (PAE) resin. As sold, the secondary amine in the polyamide and the epichlorohydrin have reacted to form a azetidnium complex as shown below. Polycup comes in a variety of different grades, where Polycup 9700 has an amine enriched polymer with the lowest DCP content and high pH so that it is compatible with both the extractables in the lignin reaction mixture and the various cross linkers. Fiber.
  • PAE polyamide-epichlorohydrin
  • wood fiber Different types are used for different applications, herein hard-wood and soft-wood fiber from mixed elm, oak, ash, hickory, maple, chestnut, birch, and poplar, and low amount of soft wood such as spruce, pine and hemlock were used. These woods are typically used in the production of medium density fiber (MDF) boards. Characteristics of the fiber product are: soft, fibrillated fluffy texture with a refined, short fibers with 10% moisture. Glyoxal. Glyoxal is a small molecule organic compound that is used in the wood/paper industries to crosslink cellulosic material in wood/paper products. Wax. Two different types of paraffin based waxes were used.
  • Chlorez 700 is a powdered solid paraffin based wax that is 70% chlorinated, that imparts both water repellency as well as some flame retardancy. During manufacture Chlorez will off-gas HCI which might play a role in the reaction of the Polycup with the lignin monomer. Also used was ULTRALUBE E345. ULTRALUBE is a registered trademark of Keim-Additec GmbH, a Federal Republic of Germany corporation, Hugo-Wagner-Strasse D-55481, Kirchberg, Germany, reg. No. 2389258.
  • ULTRALUBE E345 is a paraffin wax used for water repellency that is an emulsion with 45% solids content.
  • the molecular weight of Chlorez is approximately
  • the molecular weight of ULTRALUBE is between 280 to 420 g/mole.
  • Cyanuric is a potential alternative crosslinker to the Polycup.
  • Carbodimide is a potential alternative crosslinker to the Polycup.
  • An aminosilane specifically gamma-aminopropyltriethoxysilane, which is a potential alternative crosslinker to the Polycup.
  • a cardboard template that is 2mm thick with a cutout that is approximately 3 in x 2in is covered with aluminum foil.
  • a release agent is applied between the foil and an aluminum plate on the hot press to prevent any curing of the template to the plates of the hot press.
  • the mixture of fiber, crosslinker, liginin, and wax is placed into a mound in the center of the cardboard template, where the template is already at the cure temperature (which for these experiments is 192°C).
  • a qualitative ranking scale was employed: Poor (or 3) samples exhibited a strong yellow color in the liquid in the container; Moderate (or 2) samples showed a yellow tinted liquid; Good (or 1) samples showed little to no yellow tint in the extraction liquid. The best samples remained visually clear, indicating no leaching of unreacted material by water, which were also rated Good (or 1). Water Absorption.
  • the industry standard test requires that boards be subjected to a 24-hour period of water submersion and then dried at room humidity and temperature.
  • the ASTM D1O37-99 Standard Test Methods for Evaluating Properties of Wood-Base Fiber and Particle Panel Materials (Sections 100-103 and Sections 105-107) was employed.
  • the thickness swell and water mass absorption is observed in 24-hour intervals after the initial 24-hour submersion period. Samples that perform very well absorb the least amount of water and return to original thickness and mass after a 72-hour drying period. Note: the water adsorption test is not really concerned with how much water is absorbed, but rather how fast the water de-absorbs - this is a critical application feature, where if composite flooring or furniture get wet it returns to its original state upon drying, that has insurance implications. Pull Test. The mechanical properties of selected specimens were determined using the ASTM D952: Standard Test Method for Bond or Cohesive Strength of Sheet Plastics and Electrical Insulating Materials.
  • test c through f are all related to (a) and (b), where the simple hand screening test in (a) serves as a surrogate for (b) that can eliminate compositions that are too brittle.
  • the properties of the new lignin binder system were compared to (i) the traditional urea-formaldehdye system and (ii) for a polymeric methylene di-phenyl di- isocynante (PMDI) used in the wood composite board industry.
  • PMDI polymeric methylene di-phenyl di- isocynante
  • the composition (all by weight percent) used in industry for this system is: 77 to 84% fiber, 7% water, 8 to 15% of ureaformaldehyde (in the ratio of 1.2% formaldehyde:urea) and 0.5 to 1.5% wax.
  • the composition (all by weight percent) used in industry for this system is: 61% fiber, 15% polyethylene fiber, 12% Acurdor (BASF water-based acrylic resin), 12% Wollastonite calcium.
  • the polyethylene fibers have been added to PMDI in order to make a wood-plastic composite which is a very high end system, where the polyethylene fibers give both added strength as well as improved moisture absorption characteristics.
  • Moderate - modulus between 15 to 25 kpsi and strength modulus between 25 to 70 psia; Good - modulus greater than 25 kpsi and strength greater than psia.
  • the deligninzation reaction produces a reaction mixture that includes (i) cellulose chips from the original wood used to produce the lignin monomer and (ii) a mixture of the depolymerized lignin with some hemi-cellulose, sugars and residual methanol solvent.
  • the ‘process cellulose chips’ in Tables 1 through 4 is the cellulose from the deligninization reaction.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un procédé de réduction de phénol-formaldéhyde dans une résine et de production de stratifiés à partir de celle-ci, comprenant les étapes d'extraction d'eugénol à partir d'une source de biomasse, de mélange de l'eugénol extrait avec une première quantité d'agent de durcissement et une deuxième quantité d'eau ainsi qu'une troisième quantité de solvant MeOH en présence d'un catalyseur KOH pour produire un premier mélange, et de chauffage du premier mélange pour produire un mélange de précuisson. Le procédé comprend en outre l'ajout d'urée et d'un agent de réticulation au mélange de précuisson, l'ajout de KOH supplémentaire au mélange de précuisson pour produire un second mélange, et le chauffage du second mélange pour produire un produit de résine, le produit de résine ayant remplacé au moins environ un tiers du phénol-formaldéhyde par une résine à base d'eugénol. Ensuite, le procédé comprend le brossage du produit de résine sur des feuilles de papier respectives pour produire des feuilles respectives de papier imprégné, le séchage des feuilles respectives de papier imprégné pour produire des feuilles respectives de papier imprégné séché, l'empilement des feuilles respectives de papier imprégné séché pour produire un empilement de stratifiés à feuilles multiples, et le pressage à chaud de l'empilement de stratifiés à feuilles multiples pour produire un stratifié à feuilles multiples durci.
PCT/US2023/060901 2022-01-31 2023-01-19 Résine liante et son procédé de production WO2023147248A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223601A (en) * 1988-12-29 1993-06-29 Midwest Research Institute Ventures, Inc. Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils
US6844420B1 (en) * 1999-07-29 2005-01-18 Ensyn Renewables, Inc. Natural resin formulations
US20060079605A1 (en) * 2003-02-18 2006-04-13 Shinichi Sato Curing resin, method for producing same and curing resin composition
US20090264602A1 (en) * 2003-07-18 2009-10-22 Konishi Co., Ltd. Curable Resin Composition and Cold Setting Adhesive
JP2011148854A (ja) * 2010-01-19 2011-08-04 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223601A (en) * 1988-12-29 1993-06-29 Midwest Research Institute Ventures, Inc. Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils
US6844420B1 (en) * 1999-07-29 2005-01-18 Ensyn Renewables, Inc. Natural resin formulations
US20060079605A1 (en) * 2003-02-18 2006-04-13 Shinichi Sato Curing resin, method for producing same and curing resin composition
US20090264602A1 (en) * 2003-07-18 2009-10-22 Konishi Co., Ltd. Curable Resin Composition and Cold Setting Adhesive
JP2011148854A (ja) * 2010-01-19 2011-08-04 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物

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