WO2011138858A1 - Adhesive composition for plywood, method for producing plywood, and plywood - Google Patents

Adhesive composition for plywood, method for producing plywood, and plywood Download PDF

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Publication number
WO2011138858A1
WO2011138858A1 PCT/JP2011/002482 JP2011002482W WO2011138858A1 WO 2011138858 A1 WO2011138858 A1 WO 2011138858A1 JP 2011002482 W JP2011002482 W JP 2011002482W WO 2011138858 A1 WO2011138858 A1 WO 2011138858A1
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plywood
parts
mass
adhesive composition
weight
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PCT/JP2011/002482
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French (fr)
Japanese (ja)
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賢 清水
文男 河合
享一郎 柴谷
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株式会社コシイウッドソリューションズ
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Priority to CN2011800225601A priority Critical patent/CN102892855A/en
Publication of WO2011138858A1 publication Critical patent/WO2011138858A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/042—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/16—Wood, e.g. woodboard, fibreboard, woodchips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives

Abstract

Disclosed is a method for producing plywood wherein an adhesive composition for plywood formed by adding 1 - 15 parts by mass of acacia bark powder, 25 - 70 parts by mass of an inorganic filler, and 10 - 50 parts by mass of water to 100 parts by mass of an aqueous solution of a resole type phenol resin for which the resin part is 40 - 50% by mass is applied to single sheets, a plurality of single sheets layered and the plywood produced by applying pressure and heat. Specifically disclosed is an adhesive composition for plywood that controls puncture phenomena and dry-out problems in plywood production by controlling increases in viscosity after the preparation of the adhesive composition for plywood when single sheets with normal or low water content are used and even when single sheets with high water content are used. Also disclosed are a method for producing plywood using this adhesive composition for plywood and plywood produced by this method.

Description

合板用接着剤組成物、合板の製造方法及び合板Plywood adhesive composition, plywood manufacturing method and plywood
　本発明は、合板用接着剤組成物、合板の製造方法及び合板の技術分野に属する。 The present invention belongs to the technical field of plywood adhesive composition, plywood manufacturing method and plywood.
　従来、合板の製造に用いられる合板用接着剤組成物として、特許文献１に記載されるように、接着剤組成物の調製後の粘度増加を抑制するため、レゾール型フェノール樹脂の水溶液に、炭酸カルシウム等の無機充填材や木粉等の有機充填材を含有することが知られている。 Conventionally, as described in Patent Document 1, as an adhesive composition for plywood used in the production of plywood, an aqueous solution of a resol-type phenolic resin is used to suppress an increase in viscosity after preparation of the adhesive composition. It is known to contain an inorganic filler such as calcium and an organic filler such as wood powder.
　また、特許文献２に記載されるように、合板製造時のパンク現象を抑制するため、接着剤配合時に水の添加を極力減らす等の対策が講じられている。 Also, as described in Patent Document 2, in order to suppress the puncture phenomenon at the time of manufacturing the plywood, measures are taken such as reducing the addition of water as much as possible when the adhesive is blended.
　しかし、接着剤組成物において、水の添加を減らすと、接着剤組成物が単板に塗布されたときにドライアウトの状態になりやすく、接着力が低下するという問題がある。 However, in the adhesive composition, if the addition of water is reduced, there is a problem that when the adhesive composition is applied to a veneer, it tends to be in a dry-out state and the adhesive strength is reduced.
特開２００６－８９６７７号公報（段落００２４）JP 2006-89677 A (paragraph 0024) 特開２００４－１２３７８１号公報（段落０００１）JP 2004-123781 A (paragraph 0001)
　本発明の目的は、接着剤組成物の調製後の粘度増加が抑制され、含水率が通常あるいは低い単板を使用した場合はもとより、たとえ高含水率の単板を使用した場合であっても、合板製造時のパンク現象が抑制され、かつ、ドライアウトの問題が抑制された合板用接着剤組成物、該合板用接着剤組成物を用いる合板の製造方法、及び、該製造方法により製造された合板を提供することである。 The object of the present invention is to suppress an increase in viscosity after the preparation of the adhesive composition, not only when a veneer having a normal or low moisture content is used, but also when a veneer having a high moisture content is used. , A plywood adhesive composition in which the puncture phenomenon at the time of plywood production is suppressed and the problem of dryout is suppressed, a plywood production method using the plywood adhesive composition, and a production method Is to provide plywood.
　本発明の一局面は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～５０質量部とが添加されることにより調製されたことを特徴とする合板用接着剤組成物である。 One aspect of the present invention is that 1 to 15 parts by weight of an acacia bark powder, 25 to 70 parts by weight of an inorganic filler, 10 to 10 parts of water with respect to 100 parts by weight of a resol type phenolic resin aqueous solution having a resin content of 40 to 50% by weight. An adhesive composition for plywood prepared by adding 50 parts by mass.
　本発明の他の一局面は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１０質量部と、無機充填材２５～５０質量部と、水２５～５０質量部とが添加されることにより調製されたことを特徴とする合板用接着剤組成物である。 According to another aspect of the present invention, 1 to 10 parts by weight of an acacia bark powder, 25 to 50 parts by weight of an inorganic filler, 100 parts by weight of an aqueous resol type phenolic resin solution having a resin content of 40 to 50% by weight, water An adhesive composition for plywood, which is prepared by adding 25 to 50 parts by mass.
　本発明のさらに他の一局面は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～２５質量部とが添加されることにより調製されたことを特徴とする合板用接着剤組成物である。 According to still another aspect of the present invention, 1 to 15 parts by mass of an acacia bark powder, 25 to 70 parts by mass of an inorganic filler, and 100 parts by mass of an aqueous resol type phenolic resin solution having a resin content of 40 to 50% by mass, An adhesive composition for plywood, which is prepared by adding 10 to 25 parts by mass of water.
　本発明のさらに他の一局面は、前記合板用接着剤組成物を単板に塗布し、複数の単板を重ね合わせ、加圧、加熱することを特徴とする合板の製造方法である。 Still another aspect of the present invention is a method for manufacturing a plywood, characterized in that the adhesive composition for plywood is applied to a single plate, a plurality of single plates are overlapped, pressed and heated.
　本発明のさらに他の一局面は、前記製造方法により製造されたことを特徴とする合板である。 Still another aspect of the present invention is a plywood manufactured by the above manufacturing method.
　本発明のさらに他の一局面は、接着剤層が、硬化したフェノール樹脂４０～５０質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部とを含むことを特徴とする合板である。 Still another aspect of the present invention is that the adhesive layer contains 1 to 15 parts by mass of an acacia bark powder and 25 to 70 parts by mass of an inorganic filler with respect to 40 to 50 parts by mass of the cured phenol resin. It is a plywood featured.
　本発明の目的、特徴、局面及び利点は、以下の詳細な記載によって、より明白となるであろう。 The objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description.
　本発明者等は、アカシア植林事業から廃棄されるアカシア樹皮の有効利用を鋭意検討してきた。そして、レゾール型フェノール樹脂水溶液に、アカシア樹皮の粉末と、炭酸カルシウム等の無機充填材と、水とを加えることにより調製した糊液が、調製後の粘度増加が抑制されることを見出した。また、この糊液が、水の含有量が従来の合板用接着剤組成物に比べて相対的に多いので、ドライアウトの問題が抑制されつつ、合板製造時のパンク現象も抑制されることを見出した。さらに、本発明者等は、糊液の工業的使用の現場では想定以上の高含水率の単板（例えば含水率が１０質量％から１７質量％）が混入使用されることがあることを認め、たとえそのような場合であっても、十分な単板間の接着性を維持しつつ、ドライアウト問題を抑制し、合板製造時のパンク現象を抑制するのに必要な糊液組成を見出した。また、この糊液を用いて製造された合板は反りやうねりが抑制されることを見出した。そして、このような知見に基き、本発明を完成した。 The present inventors have intensively studied the effective use of acacia bark discarded from the acacia plantation project. And the paste liquid prepared by adding the powder of an acacia bark, inorganic fillers, such as a calcium carbonate, and water to the resol type phenol resin aqueous solution, discovered that the viscosity increase after preparation was suppressed. In addition, since this glue solution has a relatively high water content compared to the conventional adhesive composition for plywood, the problem of dryout is suppressed, and the puncture phenomenon at the time of manufacturing plywood is also suppressed. I found it. Furthermore, the present inventors have recognized that a veneer with a moisture content higher than expected (for example, a moisture content of 10% by mass to 17% by mass) may be mixed and used at the site of industrial use of the paste liquid. Even in such a case, the adhesive composition was found to be necessary to suppress the dry-out problem and suppress the puncture phenomenon during plywood production while maintaining sufficient adhesion between the single plates. . Moreover, it discovered that the plywood manufactured using this paste liquid suppressed curvature and a wave | undulation. And based on such knowledge, this invention was completed.
　以下、本発明の実施形態を説明する。ただし、本発明はこの実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to this embodiment.
　すなわち、本実施形態に係る合板用接着剤組成物は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～５０質量部とが添加されることにより調製された、合板用接着剤組成物である。 That is, the adhesive composition for plywood according to the present embodiment comprises 1 to 15 parts by mass of an acacia bark powder and 25 to 25 parts by weight of an inorganic filler with respect to 100 parts by mass of a resole type phenol resin aqueous solution having a resin content of 40 to 50% by mass. An adhesive composition for plywood prepared by adding 70 parts by mass and 10 to 50 parts by mass of water.
　この合板用接着剤組成物は、従来の合板用接着剤組成物に比べて、調製後の粘度増加が抑制される。また、含水率が通常あるいは低い単板を使用した場合はもとより、たとえ高含水率の単板を使用した場合であっても、合板製造時のパンク現象が抑制される。また、ドライアウトの問題が抑制される。さらに、製造された合板の反りやうねりが抑制される。さらに、環境性、経済性に優れる。 This plywood adhesive composition suppresses the increase in viscosity after preparation as compared with the conventional plywood adhesive composition. Moreover, the puncture phenomenon at the time of manufacturing a plywood is suppressed not only when a veneer having a normal or low moisture content is used but also when a veneer having a high moisture content is used. Moreover, the problem of dryout is suppressed. Further, warpage and undulation of the manufactured plywood are suppressed. Furthermore, it is excellent in environmental performance and economy.
　また、本実施形態に係る合板用接着剤組成物は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１０質量部と、無機充填材２５～５０質量部と、水２５～５０質量部とが添加されることにより調製された、合板用接着剤組成物である。 In addition, the adhesive composition for plywood according to the present embodiment comprises 1 to 10 parts by mass of an acacia bark powder and 25 to 25 parts by weight of an inorganic filler with respect to 100 parts by mass of a resole type phenol resin aqueous solution having a resin content of 40 to 50% by mass. An adhesive composition for plywood prepared by adding 50 parts by mass and 25 to 50 parts by mass of water.
　この合板用接着剤組成物は、特に、含水率が通常あるいは相対的に低い単板（含水率が１０質量％未満）を使用する場合に好適である。 This adhesive composition for plywood is particularly suitable when a veneer having a normal or relatively low moisture content (moisture content of less than 10% by mass) is used.
　また、本実施形態に係る合板用接着剤組成物は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～２５質量部とが添加されることにより調製された、合板用接着剤組成物である。 Further, the adhesive composition for plywood according to the present embodiment comprises 1 to 15 parts by mass of an acacia bark powder and 25 to 25 parts by weight of an inorganic filler with respect to 100 parts by mass of a resole type phenol resin aqueous solution having a resin content of 40 to 50% by mass. An adhesive composition for plywood prepared by adding 70 parts by mass and 10 to 25 parts by mass of water.
　この合板用接着剤組成物は、特に、含水率が通常あるいは相対的に低い単板（含水率が１０質量％未満）を使用する場合にも、また、含水率が相対的に高い単板（含水率が１０質量％以上）を使用する場合にも、好適である。そのため、この合板用接着剤組成物は、含水率が通常の単板、相対的に低い単板及び相対的に高い単板が混在しているような場合に、特に有用である。ただし、単板の含水率が例えば２０質量％などと高すぎると、パンク現象の発生だけでなく、フェノール樹脂の硬化や合板の接着性等にも悪影響が顕著となる。 This adhesive composition for plywood is particularly suitable for a veneer having a relatively high moisture content even when a veneer having a normal or relatively low moisture content (moisture content of less than 10% by mass) is used. It is also suitable when using a water content of 10% by mass or more. Therefore, this plywood adhesive composition is particularly useful when a single veneer having a normal moisture content, a relatively low veneer, and a relatively high veneer are mixed. However, if the water content of the veneer is too high, such as 20% by mass, not only the occurrence of the puncture phenomenon, but also the adverse effects on not only the curing of the phenol resin and the adhesiveness of the plywood are significant.
　本実施形態においては、アカシア樹皮粉末は、平均粒径が１０～１５０μｍであることが好ましい。アカシア樹皮粉末の平均粒径が１０μｍ未満であると、アカシア樹皮粉末の接着剤組成物中への分散性が低下し、１５０μｍを超えると、接着剤組成物の塗布装置が目詰まりし易くなるからである。 In this embodiment, the acacia bark powder preferably has an average particle size of 10 to 150 μm. If the average particle size of the acacia bark powder is less than 10 μm, the dispersibility of the acacia bark powder in the adhesive composition is reduced, and if it exceeds 150 μm, the coating device for the adhesive composition is easily clogged. It is.
　本実施形態においては、ポリビニルアルコール０．１～３質量部がさらに添加されていることが好ましい。ポリビニルアルコールは、単板の仮接着性を向上させたり、糊液のドライアウトを防止する効果があるからである。ポリビニルアルコールの添加量が０．１質量部未満であると、添加の有効性が低下し、３質量部を超えると、経済性が低下する。 In this embodiment, it is preferable that 0.1 to 3 parts by mass of polyvinyl alcohol is further added. This is because polyvinyl alcohol has the effect of improving the temporary adhesion of a single plate and preventing the glue solution from drying out. When the addition amount of polyvinyl alcohol is less than 0.1 parts by mass, the effectiveness of the addition decreases, and when it exceeds 3 parts by mass, the economic efficiency decreases.
　本実施形態においては、フュームドシリカ０．１～２質量部がさらに添加されていることが好ましい。フュームドシリカは、糊液の塗布作業性を向上させたり、糊液のドライアウトを抑制する効果があるからである。フュームドシリカの添加量が０．１質量部未満であると、添加の有効性が低下し、２質量部を超えると、経済性が低下する。 In this embodiment, it is preferable that 0.1 to 2 parts by mass of fumed silica is further added. This is because fumed silica has an effect of improving the application workability of the paste liquid and suppressing the dry-out of the paste liquid. When the addition amount of fumed silica is less than 0.1 parts by mass, the effectiveness of the addition is reduced, and when it exceeds 2 parts by mass, the economy is reduced.
　本実施形態に係る合板の製造方法は、前記合板用接着剤組成物を単板に塗布し、複数の単板を重ね合わせ、加圧、加熱する、合板の製造方法である。 The method for manufacturing a plywood according to this embodiment is a method for manufacturing a plywood in which the adhesive composition for plywood is applied to a single plate, a plurality of single plates are stacked, pressed, and heated.
　この合板の製造方法によれば、従来の合板用接着剤組成物に比べて調製後の粘度増加が抑制された合板用接着剤組成物を用いて合板が製造される。また、含水率が通常あるいは低い単板を使用した場合はもとより、たとえ高含水率の単板を使用した場合であっても、パンク現象が抑制される。また、ドライアウトの問題が抑制される。さらに、製造された合板の反りやうねりが抑制される。さらに、この合板の製造方法は、環境性、経済性に優れる。 According to this method for producing plywood, a plywood is produced using an adhesive composition for plywood in which an increase in viscosity after preparation is suppressed as compared with a conventional adhesive composition for plywood. Further, the puncture phenomenon is suppressed not only when a single plate having a normal or low moisture content is used but also when using a single plate having a high moisture content. Moreover, the problem of dryout is suppressed. Further, warpage and undulation of the manufactured plywood are suppressed. Furthermore, this plywood manufacturing method is excellent in environmental performance and economy.
　本実施形態に係る合板は、前記製造方法により製造された、合板である。 The plywood according to this embodiment is a plywood manufactured by the manufacturing method.
　この合板は、含水率が通常あるいは低い単板を使用した場合はもとより、たとえ高含水率の単板を使用した場合であっても、パンク現象又は接着剥離が抑制され、良好な接着力が確保され、反りやうねりが抑制された合板である。 This plywood prevents puncture or adhesion peeling and ensures good adhesion even when using a veneer with a normal or low moisture content, even when using a veneer with a high moisture content. It is a plywood in which warpage and undulation are suppressed.
　また、本実施形態に係る合板は、接着剤層が、硬化したフェノール樹脂４０～５０質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部とを含む、合板である。 In addition, the plywood according to the present embodiment is a plywood in which the adhesive layer includes 1 to 15 parts by mass of an acacia bark powder and 25 to 70 parts by mass of an inorganic filler with respect to 40 to 50 parts by mass of the cured phenol resin. It is.
　この合板の接着剤層は、硬化したフェノール樹脂４０～５０質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部とを含んでいる。これにより、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～５０質量部とが添加されることにより調製された合板用接着剤組成物が合板の製造に用いられたことが分かる。 The adhesive layer of this plywood contains 1 to 15 parts by mass of acacia bark powder and 25 to 70 parts by mass of an inorganic filler with respect to 40 to 50 parts by mass of the cured phenol resin. Thereby, 1 to 15 parts by weight of acacia bark powder, 25 to 70 parts by weight of an inorganic filler, and 10 to 50 parts by weight of water with respect to 100 parts by weight of a resole type phenol resin aqueous solution having a resin content of 40 to 50% by weight. It can be seen that the adhesive composition for plywood prepared by adding is used for the production of plywood.
　この合板の接着剤層の組成は、前記合板用接着剤組成物において、水を除く基本的な配合物であるレゾール型フェノール樹脂と、アカシア樹脂粉末と、無機充填材との配合比が規定されて硬化したものの組成である。一般に、合板製造においては、レゾール型フェノール樹脂を含む接着剤組成物に、水以外に例えば有機溶剤を添加すると、合板製造時に有機溶媒の大部分が気化し、蒸発するので、作業環境上も安全上も大きな問題を生じる。したがって、実質的に水以外の溶剤は使用されないのが通例であるから、合板の製造に用いられた水を除く接着剤組成物の組成と、製造された合板における硬化した接着剤層の組成とは、直接相関関係にあるのである。そして、もし、水１０～５０質量部が添加されない場合は、糊液の粘度が高くなりすぎ、合板製造に困難が生じる。つまり、硬化後の接着剤層が、アカシア樹皮粉末を１～１５質量部、無機充填材を２５～７０質量部というように、多量の固形分を含んだ状態で硬化するためには、接着剤組成物の段階で水を１０～５０質量部程度含んでいないと、糊液の粘度が高くなりすぎ、接着剤組成物を単板に塗布することが困難になるのである。したがって、言い換えれば、硬化後の接着剤層が、フェノール樹脂４０～５０質量部に対し、アカシア樹皮粉末を１～１５質量部、無機充填材を２５～７０質量部というように、多量の固形分を含んだ状態で硬化しているということは、接着剤組成物の段階で水を１０～５０質量部程度含んでいたということの証になるのである。 As for the composition of the adhesive layer of this plywood, the compounding ratio of the resol type phenolic resin, which is a basic composition excluding water, the acacia resin powder, and the inorganic filler in the plywood adhesive composition is defined. The composition of the cured product. In general, in plywood production, when an organic solvent other than water is added to an adhesive composition containing a resol type phenol resin, for example, most of the organic solvent evaporates and evaporates during plywood production. The above also causes a big problem. Therefore, since it is customary that substantially no solvent other than water is used, the composition of the adhesive composition excluding water used in the manufacture of the plywood, and the composition of the cured adhesive layer in the manufactured plywood Are directly correlated. If 10 to 50 parts by mass of water is not added, the viscosity of the paste becomes too high, which makes it difficult to produce plywood. That is, in order for the cured adhesive layer to cure in a state containing a large amount of solids such as 1 to 15 parts by mass of the acacia bark powder and 25 to 70 parts by mass of the inorganic filler, If the water does not contain about 10 to 50 parts by weight of water at the composition stage, the viscosity of the paste liquid becomes too high and it becomes difficult to apply the adhesive composition to a single plate. Therefore, in other words, the cured adhesive layer has a large amount of solid content such as 1 to 15 parts by weight of acacia bark powder and 25 to 70 parts by weight of inorganic filler with respect to 40 to 50 parts by weight of phenol resin. The fact that the composition is cured in a state of containing water is a proof that it contains about 10 to 50 parts by mass of water at the stage of the adhesive composition.
　パンク現象とは、合板製造時に単板の含水率が高い場合や接着剤組成物中の水の含有量が多い場合に、加圧、加熱時に発生する水蒸気により、解圧時に接着剤層に気泡が発生して接着剤層が膨らむ現象をいい、単板間の剥離が発生する現象である。 The puncture phenomenon means that when the moisture content of a veneer is high during plywood production or when the water content in the adhesive composition is high, water bubbles generated during pressurization and heating cause bubbles in the adhesive layer during decompression. Is a phenomenon in which the adhesive layer swells and the peeling between the single plates occurs.
　ドライアウトとは、合板製造時に単板に塗布された接着剤組成物から水やフェノール樹脂水溶液が多く抜けた状態をいい、この状態で糊液の塗布された単板と塗布されていない単板とを重ね合わせても、接着剤の相手方単板への転写が十分行なわれず、接着力低下の原因となる現象である。 Dryout refers to a state in which a large amount of water or aqueous phenol resin solution has been removed from the adhesive composition applied to the veneer during plywood production. Is a phenomenon that the adhesive is not sufficiently transferred to the other single plate and causes a decrease in the adhesive strength.
　本実施形態では、合板用接着剤組成物は、従来の合板用接着剤組成物に比べて、調製後の粘度増加が抑制される。これは、水添加の効果の他に、アカシア樹皮に含まれる成分が何等かの作用を及ぼしているものと考えられる。 In this embodiment, the adhesive composition for plywood suppresses the increase in viscosity after preparation as compared with the conventional adhesive composition for plywood. It is considered that this is because the components contained in the acacia bark have some effect in addition to the effect of water addition.
　本実施形態では、合板用接着剤組成物は、含水率が通常あるいは低い単板を使用した場合はもとより、たとえ高含水率の単板を使用した場合であっても、合板製造時のパンク現象が抑制される。これは、アカシア樹皮の繊維質が親水性に優れるため、接着剤組成物に含有されている水がアカシア樹皮の繊維質に吸着水として固定されることが影響していると考えられる。そのため、解圧されても気泡が発生し難いと考えられる。 In this embodiment, the adhesive composition for plywood is a puncture phenomenon during plywood production, not only when a veneer with a normal or low moisture content is used, but also when a veneer with a high moisture content is used. Is suppressed. This is considered to be because the water contained in the adhesive composition is fixed to the fiber of the acacia bark as adsorbed water because the fiber of the acacia bark is excellent in hydrophilicity. Therefore, it is considered that bubbles are hardly generated even when the pressure is released.
　本実施形態では、合板用接着剤組成物は、ドライアウトの問題が抑制される。これは、接着剤組成物の水の含有量が従来の合板用接着剤組成物に比べて相対的に多いことも影響していると考えられる。 In this embodiment, the adhesive composition for plywood suppresses the problem of dryout. This is thought to be due to the fact that the content of water in the adhesive composition is relatively large compared to the conventional adhesive composition for plywood.
　本実施形態では、前記合板用接着剤組成物を用いて製造された合板は反りやうねりが抑制される。これは、アカシア樹皮に含まれる可溶性成分の作用により、接着剤組成物に含有されている水が合板に浸透し難くなるからではないかと考えられる。 In this embodiment, the plywood manufactured using the plywood adhesive composition is suppressed from warping and undulation. This is thought to be because the water contained in the adhesive composition hardly penetrates into the plywood due to the action of the soluble component contained in the acacia bark.
　さらに、本実施形態では、合板用接着剤組成物は、従来の合板用接着剤組成物に比べて相対的に多い多量の水で希釈され、無機充填材が多量に配合されているため、接着剤組成物の単位量当たりのレゾール型フェノール樹脂の含有量が相対的に少なくなり、環境負荷が小さい、環境性に優れた接着剤組成物となる。また、経済性にも優れた接着剤組成物となる。 Furthermore, in this embodiment, the adhesive composition for plywood is diluted with a relatively large amount of water compared to the conventional adhesive composition for plywood, and a large amount of inorganic filler is blended. The content of the resol type phenolic resin per unit amount of the agent composition is relatively reduced, and the adhesive composition has a low environmental load and excellent environmental properties. Moreover, it becomes the adhesive composition excellent also in economical efficiency.
　＜レゾール型フェノール樹脂水溶液＞
　本実施形態で使用可能なレゾール型フェノール樹脂水溶液は特に限定されない。一般に、接着剤用として工業的に製造、販売されているレゾール型フェノール樹脂水溶液を特に限定することなく使用することができる。そのようなレゾール型フェノール樹脂水溶液は、一般に、後述する実施例の合成例に示すように、主として、フェノール類とアルデヒド類とを水系で水酸化ナトリウム等による強アルカリ性条件下で加熱反応させて製造されるものである。これらのフェノール樹脂水溶液は、一般的に、水系溶媒に樹脂分（固形分、不揮発分）が４０～５０質量％含まれた、粘性で、強アルカリ性の液体である。 <Resol type phenol resin aqueous solution>
The resol type phenol resin aqueous solution that can be used in the present embodiment is not particularly limited. In general, an aqueous resol-type phenol resin aqueous solution manufactured and sold industrially for adhesives can be used without any particular limitation. Such resol type phenolic resin aqueous solutions are generally produced by heating and reacting phenols and aldehydes mainly under strong alkaline conditions such as sodium hydroxide in an aqueous system, as shown in the synthesis examples of Examples described later. It is what is done. These aqueous phenol resin solutions are generally viscous and strongly alkaline liquids containing 40 to 50% by mass of a resin component (solid content and non-volatile content) in an aqueous solvent.
　レゾール型フェノール樹脂水溶液の製造方法は、前述の特許文献の他、例えば特開２００１－１５２１２０号公報等にも記載されている。レゾール型フェノール樹脂は自己反応性の官能基を有するため、加熱することによりそのまま硬化させることができる。レゾール型フェノール樹脂はそれ自体で硬化する。レゾール型フェノール樹脂は加熱によって硬化し、不溶・不融性になる。よって、合板製造用には、単に加熱するだけで硬化し、接着力及び耐水性に優れるレゾール型フェノール樹脂が好ましく用いられる。 A method for producing a resol-type phenolic resin aqueous solution is described in, for example, Japanese Patent Application Laid-Open No. 2001-152120 in addition to the above-mentioned patent documents. Since the resol type phenol resin has a self-reactive functional group, it can be cured as it is by heating. The resol type phenolic resin is cured by itself. The resol type phenolic resin is cured by heating and becomes insoluble and infusible. Therefore, for the production of plywood, a resol type phenol resin that is cured simply by heating and is excellent in adhesive strength and water resistance is preferably used.
　本実施形態で使用可能なフェノール類は特に限定されない。例えば、フェノール、クレゾール等のアルキルフェノール類；レゾルシノール、カテコール等の芳香族ジオール類；ビスフェノールＡ等のビスフェノール類；等が挙げられる。 The phenols that can be used in this embodiment are not particularly limited. For example, alkylphenols such as phenol and cresol; aromatic diols such as resorcinol and catechol; bisphenols such as bisphenol A;
　本実施形態で使用可能なアルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド等が挙げられる。 Examples of aldehydes that can be used in this embodiment include formaldehyde, paraformaldehyde, and acetaldehyde.
　本実施形態で使用可能なアルカリ性反応触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化バリウム等が挙げられる。 Examples of the alkaline reaction catalyst that can be used in this embodiment include sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide.
　フェノール類とアルデヒド類との配合比率は、得られるレゾール型フェノール樹脂の硬化速度が速くなるという観点から、（アルデヒド類／フェノール類）のモル比で１以上が好ましい。また、製造した合板からのアルデヒド類の放出が少なく、生産環境が良好となるという観点から、（アルデヒド類／フェノール類）のモル比で３．５以下が好ましい。本実施形態では、特に、（アルデヒド類／フェノール類）のモル比は、１．８～２．８がより好ましい。 The blending ratio of phenols and aldehydes is preferably 1 or more in terms of (aldehydes / phenols) molar ratio from the viewpoint of increasing the curing rate of the resulting resol type phenol resin. Further, from the viewpoint that the release of aldehydes from the manufactured plywood is small and the production environment is good, the molar ratio of (aldehydes / phenols) is preferably 3.5 or less. In the present embodiment, in particular, the molar ratio of (aldehydes / phenols) is more preferably 1.8 to 2.8.
　本実施形態で使用可能なレゾール型フェノール樹脂は、耐水性の高い接着剤組成物を提供する。本実施形態では、レゾール型フェノール樹脂の１種を単独で又は２種以上を組み合わせて使用することができる。 The resol type phenolic resin that can be used in this embodiment provides an adhesive composition with high water resistance. In the present embodiment, one type of resol type phenol resin can be used alone or in combination of two or more types.
　＜アカシア樹皮粉末＞
　本実施形態で使用可能なアカシア樹皮粉末は特に限定されない。例えば、アカシアマンギューム樹皮、アカシアハイブリッド樹皮、モリシマアカシア樹皮等の粉末が挙げられる。これらのうちでは、アカシアマンギューム樹皮の粉末が好ましい。 <Acacia bark powder>
The acacia bark powder that can be used in the present embodiment is not particularly limited. Examples thereof include powders such as acacia mangum bark, acacia hybrid bark, and Morishima acacia bark. Of these, acacia mangum bark powder is preferred.
　アカシア樹皮には、メタノール抽出分（メタノールで抽出されるポリフェノールであるタンニンを含む抽出分）の含有量が相対的に高い（例えば３０％程度）外樹皮と、相対的に低い内樹皮とがあるが、本実施形態では、外樹皮と内樹皮との分離は必要ではない。使用するアカシア樹皮のタンニン含有量は、本発明者等の知見によれば、本発明の効果に大きな影響は与えない。すなわち、本実施形態では、外樹皮のみの粉末、内樹皮のみの粉末、外樹皮の粉末と内樹皮の粉末との混合物のいずれも好ましく使用可能である。工業的には、外樹皮と内樹皮とを分離することなく粉砕した平均粒径が１５０μｍ以下のアカシアマンギューム樹皮粉末であって、メタノール抽出分が２０％程度のものが、経済的観点から好ましいものの１つである。 Acacia bark has an outer bark with a relatively high content (for example, about 30%) of the methanol extract (an extract containing tannin, a polyphenol extracted with methanol), and an inner bark with a relatively low content. However, in this embodiment, it is not necessary to separate the outer bark and the inner bark. According to the knowledge of the present inventors, the tannin content of the acacia bark used does not significantly affect the effect of the present invention. That is, in the present embodiment, any of powder of only outer bark, powder of only inner bark, and a mixture of powder of outer bark and powder of inner bark can be preferably used. Industrially, it is an acacia mangum bark powder having an average particle size of 150 μm or less that has been crushed without separating the outer bark and inner bark, and has a methanol extract of about 20%, from an economic point of view. One of the preferred ones.
　アカシア樹皮粉末の製造方法の一工程である樹皮の粉砕方法は特に限定されない。例えば、ボールミル型粉砕機を用いる粉砕方法等が挙げられる。 The method for pulverizing bark, which is one step in the method for producing acacia bark powder, is not particularly limited. Examples thereof include a pulverization method using a ball mill type pulverizer.
　本実施形態では、アカシア樹皮粉末の平均粒径は、接着剤組成物の単板への塗布装置（例えばスプレッダー等）での目詰まりが防がれるという観点から、１５０μｍ以下が好ましく、１００μｍ以下がより好ましく、５０μｍ以下がさらに好ましく、３０μｍ以下がさらに好ましい。また、アカシア樹皮粉末の接着剤組成物中への分散が容易となるという観点から、１０μｍ以上が好ましい。 In the present embodiment, the average particle size of the acacia bark powder is preferably 150 μm or less, and preferably 100 μm or less from the viewpoint of preventing clogging of the adhesive composition on a single plate with a device (for example, a spreader). More preferably, it is 50 μm or less, more preferably 30 μm or less. Moreover, 10 micrometers or more are preferable from a viewpoint that the dispersion | distribution in the adhesive composition of an acacia bark powder becomes easy.
　本実施形態では、アカシア樹皮粉末の１種を単独で又は２種以上を組み合わせて使用することができる。 In this embodiment, one kind of acacia bark powder can be used alone or in combination of two or more kinds.
　本実施形態では、アカシア樹皮粉末は、パンク現象の抑制にも寄与する。 In this embodiment, the acacia bark powder also contributes to the suppression of the puncture phenomenon.
　＜無機充填材＞
　本実施形態で使用可能な無機充填材としては、例えば、炭酸カルシウム、シリカ、珪藻土、カオリン、石膏、クレー、水酸化アルミニウム等が挙げられる。これらのうちでは、接着剤組成物の硬化物（すなわち合板となった後の接着剤層）の強度や硬度、及び経済性の観点から、炭酸カルシウムが好ましい。 <Inorganic filler>
Examples of the inorganic filler that can be used in the present embodiment include calcium carbonate, silica, diatomaceous earth, kaolin, gypsum, clay, and aluminum hydroxide. Among these, calcium carbonate is preferable from the viewpoint of the strength and hardness of the cured product of the adhesive composition (that is, the adhesive layer after becoming a plywood) and economy.
　本実施形態では、無機充填材の平均粒径は、接着剤組成物の単板への塗布装置（例えばスプレッダー等）での目詰まりが防がれるという観点から、１５０μｍ以下が好ましく、１００μｍ以下がより好ましく、５０μｍ以下がさらに好ましく、３０μｍ以下がさらに好ましく、１０μｍ以下がさらに好ましい。１０μｍ以下の微粉末状の無機充填材は商業的に容易に入手できる。また、無機充填材の接着剤組成物中への分散が容易となるという観点から、１μｍ以上が好ましい。 In the present embodiment, the average particle size of the inorganic filler is preferably 150 μm or less, and preferably 100 μm or less from the viewpoint of preventing clogging of the adhesive composition on a single plate with a device (for example, a spreader). More preferably, it is 50 μm or less, more preferably 30 μm or less, and further preferably 10 μm or less. An inorganic filler in the form of fine powder of 10 μm or less can be easily obtained commercially. Moreover, 1 micrometer or more is preferable from a viewpoint that the dispersion | distribution in the adhesive composition of an inorganic filler becomes easy.
　本実施形態では、無機充填材の１種を単独で又は２種以上を組み合わせて使用することができる。その場合、炭酸カルシウムを必須成分としなくてもよいが、状況によっては、炭酸カルシウムを必須成分とすると良い結果が得られる場合が多い。 In this embodiment, one kind of inorganic filler can be used alone or in combination of two or more kinds. In that case, calcium carbonate may not be an essential component, but depending on the situation, good results are often obtained when calcium carbonate is an essential component.
　＜水＞
　本実施形態において、レゾール型フェノール樹脂水溶液１００質量部に対して１０～５０質量部と従来の合板用接着剤組成物に比べて相対的に多量に使用する水としては、イオン交換水が好ましい。接着剤組成物を含水率が通常あるいは相対的に低い単板（例えば１０質量％未満、例えば８質量％等）に適用する場合は、パンク発生率抑制のため、水添加量はレゾール型フェノール樹脂水溶液１００質量部に対して２５～５０質量部が好ましく、含水率が相対的に高い単板（例えば１０質量％以上、例えば１０～１７質量％等）に適用する場合は、パンク発生率抑制のため、水添加量はレゾール型フェノール樹脂水溶液１００質量部に対して１０～２５質量部が好ましいことが見出された。ただし、水添加量が１０～２５質量部の接着剤組成物を含水率が通常あるいは相対的に低い単板に適用しても構わない。また、水添加量が１０～５０質量部の範囲にある接着剤組成物であれば、状況に応じて、単板の含水率に限定されず、含水率が通常あるいは相対的に低い単板に適用することもできるし、含水率が相対的に高い単板に適用することもできる。 <Water>
In the present embodiment, ion-exchanged water is preferable as water used in a relatively large amount of 10 to 50 parts by mass with respect to 100 parts by mass of the resol type phenolic resin aqueous solution as compared with the conventional adhesive composition for plywood. When the adhesive composition is applied to a veneer having a normal or relatively low moisture content (for example, less than 10% by mass, for example, 8% by mass), the amount of water added is a resol type phenolic resin in order to suppress the occurrence of puncture. 25 to 50 parts by mass with respect to 100 parts by mass of the aqueous solution, and when applied to a single plate having a relatively high water content (eg, 10% by mass or more, eg, 10 to 17% by mass), the puncture generation rate is suppressed. Therefore, it was found that the amount of water added is preferably 10 to 25 parts by mass with respect to 100 parts by mass of the resol type phenol resin aqueous solution. However, an adhesive composition having a water addition amount of 10 to 25 parts by mass may be applied to a veneer having a normal or relatively low water content. Further, if the adhesive composition has an amount of water added in the range of 10 to 50 parts by mass, it is not limited to the moisture content of the veneer depending on the situation, and the moisture content is usually or relatively low. It can also be applied, or it can be applied to a veneer having a relatively high moisture content.
　＜作用機構＞
　本発明者等は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液に水を加え、この希釈溶液にアカシア樹皮粉末を加えると、希釈溶液の粘度が塗布するのに適した粘度までやや上昇し、硬化速度がやや増加するという知見を得た。すなわち、水で希釈された糊液が得られた。しかし、このフェノール樹脂含有量の相対的に低い糊液は、表面の粗度（凹凸）が相対的に大きい単板に塗布し接合したときは、十分な接着力を与えることができなかった。 <Action mechanism>
When the present inventors add water to a resol type phenolic resin aqueous solution having a resin content of 40 to 50% by mass and add acacia bark powder to this diluted solution, the viscosity of the diluted solution is slightly increased to a viscosity suitable for application. As a result, it was found that the curing rate slightly increased. That is, a paste liquid diluted with water was obtained. However, when the paste solution having a relatively low phenol resin content is applied to and bonded to a single plate having a relatively large surface roughness (unevenness), it cannot provide a sufficient adhesive force.
　本発明者等は、このフェノール樹脂含有量の相対的に低い糊液に、無機充填材を加えると、一般的な単板に対する糊液塗布量（３５～４０ｇ／ｆｔ２、すなわち３７～４３ｍｇ／ｃｍ２）において、良好な接着力が得られることを見出した。 When the present inventors added an inorganic filler to the paste solution having a relatively low phenol resin content, the amount of paste solution applied to a general veneer (35 to 40 g / ft 2 , ie 37 to 43 mg / It was found that a good adhesive force can be obtained at cm 2 ).
　＜配合比率＞
　本実施形態に係る合板用接着剤組成物において、最適の配合比率は適用する単板の含水率に応じて変わることが認められるが、好ましい配合比率は、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部、無機充填材２５～７０質量部、水１０～５０質量部である。単板の含水率が通常あるいは相対的に低い場合（例えば１０質量％未満）は、水の添加量は多く、アカシア樹皮粉末の添加量は少なく、無機充填材の添加量は少ないことが、パンク発生を抑制しつつ、高い接着力が得られる等、好ましい性能が得られることが見出され、一方、単板の含水率が相対的に高い場合（例えば１０質量％以上）は、水の添加率は少なく、アカシア樹皮粉末の添加量は多く、無機充填材の添加量は多いことが、パンク発生を抑制しつつ、高い接着力が得られる等、好ましい性能が得られることが見出された。このような配合比率で調製した糊液は、経済性、糊液粘度、糊液粘度の経時安定性、合板用接着剤組成物としての高い耐水性及び高い接着性等の種々の性能がバランスよく発揮される。 <Combination ratio>
In the adhesive composition for plywood according to this embodiment, it is recognized that the optimum blending ratio varies depending on the moisture content of the veneer to be applied, but the preferred blending ratio is a resole having a resin content of 40 to 50% by mass. The amount of the acacia bark powder is 1 to 15 parts by mass, the inorganic filler is 25 to 70 parts by mass, and the water is 10 to 50 parts by mass with respect to 100 parts by mass of the aqueous phenol resin solution. When the moisture content of a veneer is normal or relatively low (for example, less than 10% by mass), the amount of water added is large, the amount of acacia bark powder added is small, and the amount of inorganic filler added is small. It has been found that preferable performance can be obtained such as high adhesive force while suppressing generation, while water content of the veneer is relatively high (for example, 10% by mass or more), the addition of water It has been found that favorable performance can be obtained such as high adhesion strength while suppressing the occurrence of puncture, with a low rate, a large amount of acacia bark powder added, and a large amount of inorganic filler added. . The paste solution prepared with such a blending ratio is well balanced in various performances such as economy, paste solution viscosity, stability over time of paste solution viscosity, high water resistance and high adhesiveness as an adhesive composition for plywood. Demonstrated.
　レゾール型フェノール樹脂水溶液に添加して良好な性能が発揮される３種類の成分（アカシア樹皮粉末、水、無機充填材）の配合量は相互に関連しているので、添加する各成分の量と発揮される性能とを個別に明らかにすることは困難であるが、以下のことが明らかである。 The amount of the three components (acacia bark powder, water, and inorganic filler) that can be added to the resol-type phenolic resin aqueous solution to achieve good performance are related to each other. It is difficult to clarify the performance to be exhibited individually, but the following is clear.
　（アカシア樹皮粉末の配合量）
　樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末の配合量を１質量部以上とすることにより、糊液の粘度が塗布するのに適した粘度まで上昇することがより一層確実となる。また、アカシア樹皮粉末の配合量を一般的には１０質量部以下とすることにより、糊液の経済性が確保されるが、高含水率の単板が混入使用される場合には、パンクを抑制して接着力の向上を図るため、アカシア樹皮粉末の配合量を１５質量部以下まで増加することも選択可能である。アカシア樹皮粉末の配合量を１５質量部超えにすることは経済性から好ましくない。一般的には、レゾール型フェノール樹脂水溶液１００質量部に対するアカシア樹皮粉末の好ましい配合量は２～６質量部である。 (Amount of acacia bark powder)
By adding 1 part by weight or more of acacia bark powder to 100 parts by weight of a resole phenolic resin aqueous solution with a resin content of 40 to 50% by weight, the viscosity of the paste increases to a viscosity suitable for application. It is even more certain to do. The amount of acacia bark powder is generally 10 parts by mass or less, so that the economy of the paste liquid is ensured. However, if a single board with a high water content is mixed and used, puncture is required. In order to suppress and improve the adhesive strength, it is also possible to select to increase the blending amount of the acacia bark powder to 15 parts by mass or less. It is not preferable from the economical point of view that the amount of the acacia bark powder exceeds 15 parts by mass. In general, the preferable blending amount of the acacia bark powder with respect to 100 parts by mass of the resol type phenol resin aqueous solution is 2 to 6 parts by mass.
　（水の配合量）
　レゾール型フェノール樹脂水溶液にアカシア樹皮粉末を配合することにより多量の水を配合できるようになったことは、本発明の特徴の１つである。樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、一般的な単板の使用時には、水の配合量を２５質量部以上とすることにより、ドライアウト抑制効果、環境負荷低減効果、経済性向上効果等が発揮される。一方、高含水率の単板が混入使用される場合には、水の配合量を１０～２５質量部とすることにより、これらの効果を維持することができる。水の配合量が１０質量部未満となると、本発明の目的の１つである経済性が十分に発揮できない。また、水の配合量を５０質量部以下とすることにより、無機充填材の大量配合を回避することができる。つまり、レゾール型フェノール樹脂水溶液１００質量部に対する水の配合量が５０質量部を超えると、その糊液は、一般的な糊液塗布量では、単板上に固形分が確保され難くなるのである。そして、その場合は、無機充填材を大量に配合することにより、単板上に固形分が確保されるように対処するのであるが、無機充填材の大量配合は糊液の塗工性を損ない、接着力低下を招き易くなる。また、糊液塗布後、短時間で、接合、加圧、加熱を行なっても、接着力不足が生じ易くなる。すなわち、レゾール型フェノール樹脂水溶液１００質量部に対する水の配合量を５０質量部以下とすることにより、無機充填材の大量配合が回避でき、糊液塗工性を維持し、十分な接着力を得ることができる。 (Water content)
It is one of the features of the present invention that a large amount of water can be added by adding an acacia bark powder to a resol type phenolic resin aqueous solution. When using a general veneer for 100 parts by mass of a resole-type phenolic resin aqueous solution with a resin content of 40 to 50% by mass, by controlling the amount of water to 25 parts by mass or more, the effect of suppressing dryout and environmental impact Reduction effect, economic improvement effect, etc. are exhibited. On the other hand, when a high moisture content veneer is mixed and used, these effects can be maintained by setting the blending amount of water to 10 to 25 parts by mass. If the blending amount of water is less than 10 parts by mass, the economic efficiency, which is one of the objects of the present invention, cannot be sufficiently exhibited. Moreover, a large amount of inorganic filler can be avoided by setting the amount of water to 50 parts by mass or less. That is, when the blending amount of water with respect to 100 parts by mass of the resol-type phenol resin aqueous solution exceeds 50 parts by mass, it is difficult to secure a solid content on the veneer with a general adhesive liquid application amount. . In that case, a large amount of inorganic filler is mixed so that solid content is secured on the veneer. However, a large amount of inorganic filler impairs the coating property of the paste liquid. , It tends to cause a decrease in adhesive strength. Moreover, even if bonding, pressurization, and heating are performed in a short time after applying the paste liquid, insufficient adhesive strength is likely to occur. That is, by setting the amount of water to 50 parts by mass or less based on 100 parts by mass of the resol type phenolic resin aqueous solution, a large amount of inorganic filler can be avoided, the paste coating property is maintained, and sufficient adhesive strength is obtained. be able to.
　（無機充填材の配合量）
　無機充填材の適切な配合量は、単板の含水量による他、アカシア樹皮粉末の配合量や水の配合量に相関する。そして、レゾール型フェノール樹脂水溶液１００質量部に対し、無機充填材の配合量を２５質量部以上とすることにより、フェノール樹脂含有量が相対的に低いにも拘らず、一般的な単板に対する糊液塗布量で良好な接着力が得られるという前述の効果がより一層発揮される。また、高含水率単板であっても、無機充填材の配合量を７０質量部以下の高配合量とすることにより、前述したように、ドライアウトに起因する接着力低下、樹脂の硬化不良に起因する接着力不足の問題が回避される。糊液の塗工性がよく、接着力を高く維持するためには無機充填材の配合量を６０質量部以下とすることが一層好ましい。レゾール型フェノール樹脂水溶液１００質量部に対する無機充填材のより好ましい配合量は、通常の単板の場合は、２５～５０質量部、より好ましくは３０～４５質量部であるが、高含水率単板が混入使用されるような場合は、水、アカシア樹皮粉末の配合量によっては、４５～６０質量部、さらには４５～５５質量部、さらには３５～５５質量部が好ましい場合がある。 (Inorganic filler content)
The appropriate blending amount of the inorganic filler is correlated with the blending amount of the acacia bark powder and the blending amount of water in addition to the water content of the veneer. And by making the compounding quantity of an inorganic filler into 25 mass parts or more with respect to 100 mass parts of resol type phenol resin aqueous solution, although the phenol resin content is relatively low, the paste for a general veneer The above-described effect that a good adhesive force can be obtained with a liquid application amount is further exhibited. Moreover, even with a high moisture content veneer, by reducing the blending amount of the inorganic filler to a high blending amount of 70 parts by mass or less, as described above, the adhesive strength is reduced due to dryout, and the resin is not cured properly. The problem of insufficient adhesive force due to the is avoided. It is more preferable that the blending amount of the inorganic filler is 60 parts by mass or less in order to maintain good adhesive strength and high adhesion. A more preferable blending amount of the inorganic filler with respect to 100 parts by mass of the resol type phenolic resin aqueous solution is 25 to 50 parts by mass, more preferably 30 to 45 parts by mass in the case of a normal veneer, but a high moisture content veneer May be mixed depending on the amount of water and acacia bark powder, 45 to 60 parts by mass, further 45 to 55 parts by mass, and further 35 to 55 parts by mass may be preferable.
　（好ましい配合の具体例）
　以上のような理由により、本実施形態に係る合板用接着剤組成物の好ましい配合の具体例は、例えば含水率８質量％程度の通常含水率の単板に対しては、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、平均粒径が１０～３０μｍでメタノール抽出分が２０％程度のアカシアマンギューム樹皮粉末２～６質量部と、平均粒径が１～１０μｍの炭酸カルシウム３０～４５質量部と、水２５～５０質量部とが添加されることにより調製された合板用接着剤組成物である。一方、含水率１０質量％以上の高含水率単板を含む単板を使用する場合には、樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、平均粒径が１０～３０μｍでメタノール抽出分が２０％程度のアカシアマンギューム樹皮粉末３～１０質量部と、平均粒径が１～１０μｍの炭酸カルシウム３０～６０質量部と、水１５～２５質量部とが添加されることにより調製された合板用接着剤組成物が好ましい配合の具体例である。含水率１０質量％以上の高含水率単板を含む単板を使用する場合の一層好ましい配合の具体例は、アカシアマンギューム樹皮粉末５～１０質量部、炭酸カルシウム３５～５５質量部、水１５～２０質量部を含むものである。 (Specific examples of preferred formulations)
For the reasons described above, a specific example of a preferable composition of the adhesive composition for plywood according to the present embodiment is, for example, a resin content of 40 to 40% for a normal moisture content veneer having a moisture content of about 8% by mass. 2 to 6 parts by weight of an acacia mangum bark powder having an average particle size of 10 to 30 μm and a methanol extract of about 20% with respect to 100 parts by weight of a 50% by weight resol type phenolic resin aqueous solution; An adhesive composition for plywood prepared by adding 30 to 45 parts by mass of 10 μm calcium carbonate and 25 to 50 parts by mass of water. On the other hand, when a veneer including a high moisture content veneer having a water content of 10% by mass or more is used, the average particle size is 10 parts per 100 parts by mass of the resol type phenol resin aqueous solution having a resin content of 40 to 50% by mass. 3 to 10 parts by weight of acacia mangum bark powder with a methanol extract of about 20% at 30 μm, 30 to 60 parts by weight of calcium carbonate with an average particle size of 1 to 10 μm, and 15 to 25 parts by weight of water are added The adhesive composition for plywood prepared as described above is a specific example of a preferred formulation. Specific examples of a more preferable composition when using a veneer containing a high moisture content veneer having a water content of 10% by mass or more include 5 to 10 parts by mass of acacia mangum bark powder, 35 to 55 parts by mass of calcium carbonate, water It contains 15 to 20 parts by mass.
　（３種類の成分の配合量の相関式）
　本実施形態においては、レゾール型フェノール樹脂水溶液１００質量部に対する３種類の成分の適切な配合量は相関関係にあり、含水率８質量％程度の通常含水率の単板に対しては、およそ以下のような配合量の組合せが、糊液性能、接着性能の観点から好ましい。
・アカシア樹皮粉末　０．１Ｘ±２質量部
・無機充填材　Ｘ質量部（Ｘ：２５～５０、好ましくは３０～４５）
・水　Ｘ±５質量部 (Correlation formula of blending amounts of three types of ingredients)
In the present embodiment, the appropriate blending amounts of the three components with respect to 100 parts by mass of the resol-type phenol resin aqueous solution are correlated, and for a normal moisture content veneer having a moisture content of about 8% by mass, Such a combination of blending amounts is preferable from the viewpoints of paste performance and adhesive performance.
Acacia bark powder 0.1X ± 2 parts by mass Inorganic filler X parts by mass (X: 25 to 50, preferably 30 to 45)
・ Water X ± 5 parts by mass
　一方、含水率１０質量％以上の高含水率単板が混入する場合は、以下のような数式で与えられる配合量の組み合わせの中にある配合量が、パンク発生の抑制、糊液性能、接着性能の観点から好ましい。
・アカシア樹皮粉末　０．２Ｘ±２質量部
・無機充填材　Ｘ質量部（Ｘ：２５～７０、好ましくは３５～５５）
・水　０．４Ｘ±５質量部 On the other hand, when a high moisture content veneer with a moisture content of 10% by mass or more is mixed, the compounding amount in the combination of the compounding amounts given by the following mathematical formulas suppresses the occurrence of puncture, paste liquid performance, adhesion It is preferable from the viewpoint of performance.
Acacia bark powder 0.2X ± 2 parts by massInorganic filler X parts by mass (X: 25 to 70, preferably 35 to 55)
・ Water 0.4X ± 5 parts by mass
　＜その他の添加剤＞
　（ポリビニルアルコール）
　本実施形態においては、状況に応じて、合板用接着剤組成物に、ポリビニルアルコール（ＰＶＡと記す場合がある）を配合してもよい。ＰＶＡは、単板に糊液を塗布し、単板を重ね合わせて接合し、冷間（室温）において加圧し（冷圧）するときの仮接着性を向上させ、仮接着の作業性を向上させる観点から好ましい添加剤である。また、後述する実施例における合板の接着力評価（接着試験）からは、糊液のドライアウトを防止して接着力を確保する効果のあることが認められる。 <Other additives>
(Polyvinyl alcohol)
In this embodiment, you may mix | blend polyvinyl alcohol (it may be described as PVA) with the adhesive composition for plywood according to a condition. PVA applies adhesive solution to single plates, stacks and bonds the single plates, improves temporary adhesion when cold (room temperature) is pressurized (cold pressure), and improves temporary bonding workability From the viewpoint of making it a preferable additive. Moreover, it is recognized from the adhesive force evaluation (adhesion test) of the plywood in the Example mentioned later that there exists an effect which prevents the dry-out of a paste liquid and ensures adhesive force.
　ＰＶＡの重合度は、例えば１７００程度まで大きいことが、接着力確保の効果が発現され易いという観点から好ましい。ただし、ＰＶＡの溶解時間や溶解作業性を考慮すると、重合度が５００程度の部分ケン化物の細粒が好ましい。そのようなものとしては、例えば、クラレ社製の「ＰＶＡ－２０５Ｓ」（ケン化度：８６．５～８９モル％）等が好適である。 The polymerization degree of PVA is preferably as large as about 1700, for example, from the viewpoint that the effect of securing adhesive force is easily exhibited. However, considering the dissolution time and dissolution workability of PVA, fine particles of a partially saponified product having a degree of polymerization of about 500 are preferred. For example, “PVA-205S” (degree of saponification: 86.5 to 89 mol%) manufactured by Kuraray is suitable.
　レゾール型フェノール樹脂水溶液１００質量部に対するＰＶＡの配合量は、有効性と経済性とのバランスの観点から、０．１～３質量部が好ましく、０．１～１質量部がより好ましく、０．２～０．６質量部がさらに好ましい。 The blending amount of PVA with respect to 100 parts by mass of the resol type phenol resin aqueous solution is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass, from the viewpoint of balance between effectiveness and economy. 2 to 0.6 parts by mass is more preferable.
　（フュームドシリカ）
　本実施形態においては、状況に応じて、合板用接着剤組成物に、フュームドシリカを配合してもよい。フュームドシリカは、単板に糊液を塗布するときの塗布作業性を向上させ、かつ、糊液のドライアウトを抑制する観点から好ましい添加剤である。フュームドシリカには、比表面積が１００～４００ｍ２／ｇ程度までのものがあり、また、各種の表面処理が施されたものがある。本実施形態では、親水性表面で、比表面積が２００ｍ２／ｇ程度のものが好ましい。そのようなものとしては、例えば、日本アエロジル社製の親水性フュームドシリカ「ＡＥＲＯＳＩＬ（登録商標）２００」等が好適である。 (Fumed silica)
In this embodiment, you may mix | blend fumed silica with the adhesive composition for plywood according to a condition. Fumed silica is a preferred additive from the viewpoint of improving the coating workability when applying the paste liquid to a single plate and suppressing the dry-out of the paste liquid. Some fumed silicas have a specific surface area of up to about 100 to 400 m 2 / g, and some have undergone various surface treatments. In the present embodiment, a hydrophilic surface having a specific surface area of about 200 m 2 / g is preferable. For example, hydrophilic fumed silica “AEROSIL (registered trademark) 200” manufactured by Nippon Aerosil Co., Ltd. is suitable.
　レゾール型フェノール樹脂水溶液１００質量部に対するフュームドシリカの配合量は、有効性と経済性とのバランスの観点から、０．１～２質量部が好ましく、０．３～１質量部がより好ましく、０．３～０．６質量部がさらに好ましい。 The blended amount of fumed silica with respect to 100 parts by mass of the resol type phenol resin aqueous solution is preferably 0.1 to 2 parts by mass, more preferably 0.3 to 1 part by mass from the viewpoint of balance between effectiveness and economy. More preferred is 0.3 to 0.6 parts by mass.
　（粘度調整剤）
　本実施形態においては、状況に応じて、合板用接着剤組成物に、例えば小麦粉等の粘度調整剤を配合してもよい。 (Viscosity modifier)
In this embodiment, you may mix | blend viscosity modifiers, such as flour, for example with the adhesive composition for plywood according to a condition.
　（硬化促進剤）
　本実施形態においては、状況に応じて、合板用接着剤組成物に、例えば炭酸ナトリウムや重炭酸ナトリウム等の硬化促進剤を配合してもよい。 (Curing accelerator)
In this embodiment, you may mix | blend hardening accelerators, such as sodium carbonate and sodium bicarbonate, for example with the adhesive composition for plywood according to a condition.
　（その他）
　本実施形態においては、状況に応じて、合板用接着剤組成物に、例えばヤシガラ粉末等の有機系充填材や、ホルムアルデヒドの放散を抑制するためのホルムアルデヒドキャッチャ等を配合してもよい。 (Other)
In the present embodiment, depending on the situation, the plywood adhesive composition may be blended with, for example, an organic filler such as coconut shell powder or a formaldehyde catcher for suppressing formaldehyde emission.
　＜合板用接着剤組成物の調製方法＞
　一般に、レゾール型フェノール樹脂は、合成直後から硬化が始まり、合板工場で使用されるまでの期間中に、粘度上昇が起き易い。そのような粘度が上昇したレゾール型フェノール樹脂に、アカシア樹皮粉末や無機充填材等の粉体成分を順に添加し、混合することは作業性に劣る。そこで、本実施形態においては、粉体成分（アカシア樹皮粉末、無機充填材、ＰＶＡ、フュームドシリカ、小麦粉等）を予め混合しておき、合板工場では、レゾール型フェノール樹脂と、水と、予め混合しておいた粉体成分とを混合することにより、糊液を調製することが作業効率の観点から好ましい。その場合、経時変化し、粘度が上昇したレゾール型フェノール樹脂の粘度に応じて、粘度調整剤としての小麦粉等を別に添加するようにしてもよい。 <Preparation method of adhesive composition for plywood>
In general, a resol type phenolic resin starts to cure immediately after synthesis and tends to increase in viscosity during a period until it is used in a plywood factory. It is inferior in workability to add and mix powder components such as acacia bark powder and inorganic filler in order to such a resol type phenolic resin having an increased viscosity. Therefore, in this embodiment, powder components (acacia bark powder, inorganic filler, PVA, fumed silica, wheat flour, etc.) are mixed in advance, and in the plywood factory, resol type phenolic resin, water, From the viewpoint of work efficiency, it is preferable to prepare a paste liquid by mixing the powder component that has been mixed. In that case, you may make it add flour etc. as a viscosity regulator separately according to the viscosity of the resol type phenol resin which changed with time and the viscosity increased.
　工業的に製造、販売されるレゾール型フェノール樹脂は、一般に、樹脂分が４０～５０質量％に調整されている。これを用いて接着剤組成物を調製する場合、レゾール型フェノール樹脂の合成の後工程において、本実施形態で規定される一部の水又は全部の水を予め加えて、接着剤組成物の調製現場に輸送し、ここで残りの成分を加えて接着剤組成物を完成してもよい。このような調製方法は、輸送や保管期間中の樹脂粘度上昇を抑制する利点が存在する。さらに、レゾール型フェノール樹脂の合成後に、本実施形態で規定される一部の水又は全部の水の他、その他の成分を一部加えてもよい。また、水を含む全成分をレゾール型フェノール樹脂に添加して接着剤組成物を調製し、これを合板工場に輸送して合板工場でそのまま使用してもよい。 In general, resol type phenolic resins manufactured and sold industrially have a resin content adjusted to 40 to 50% by mass. When preparing an adhesive composition using this, in the post-process of synthesizing a resol type phenol resin, a part or all of the water defined in the present embodiment is added in advance to prepare an adhesive composition. It may be transported to the site where the remaining ingredients may be added to complete the adhesive composition. Such a preparation method has an advantage of suppressing an increase in resin viscosity during transportation and storage. Furthermore, after synthesizing the resol type phenol resin, a part of other components may be added in addition to a part of water or the whole water specified in the present embodiment. Moreover, all the components containing water may be added to a resol type phenol resin to prepare an adhesive composition, which may be transported to a plywood factory and used as it is in a plywood factory.
　＜合板の製造方法＞
　本実施形態においては、前記合板用接着剤組成物を用いて合板を製造する。すなわち、前記合板用接着剤組成物を単板に塗布し、複数の単板を重ね合わせ、加圧、加熱することにより、合板を得ることができる。まず、例えばスプレッダー等の塗布装置を用いて前記接着剤組成物を単板に塗布する。次に、所定の枚数の単板同士を重ね合わせる。冷間（室温）において、例えば１．０ＭＰａに加圧し（冷圧）、仮接着した複数の単板を、例えば１．０ＭＰａに加圧しつつ、例えば１２０～１４０℃に加熱し（熱圧）、接着剤組成物を硬化させる方法が挙げられる。熱圧時の加熱温度が不足すると、接着剤組成物の硬化に時間がかかり過ぎ、合板の生産効率が低下し、経済性が低下する。熱圧時の加熱温度が高すぎると、パンク現象が起こり易くなる。平地での熱圧時の好ましい加熱温度は、例えば１２５～１３０℃である。 <Manufacturing method of plywood>
In this embodiment, a plywood is manufactured using the adhesive composition for plywood. That is, a plywood can be obtained by applying the adhesive composition for plywood to a single plate, stacking a plurality of single plates, pressing and heating. First, the adhesive composition is applied to a single plate using an application device such as a spreader. Next, a predetermined number of single plates are overlapped. In cold (room temperature), for example, pressurized to 1.0 MPa (cold pressure), a plurality of temporarily bonded single plates, for example, heated to 120-140 ° C. while being pressurized to 1.0 MPa (hot pressure), A method for curing the adhesive composition is exemplified. If the heating temperature at the time of hot pressing is insufficient, it takes too much time to cure the adhesive composition, the production efficiency of the plywood is lowered, and the economic efficiency is lowered. If the heating temperature at the time of hot pressing is too high, the puncture phenomenon tends to occur. A preferable heating temperature at the time of hot pressing on a flat ground is, for example, 125 to 130 ° C.
　以上のように、本明細書は様々な態様を開示している。本明細書が開示する態様によれば、接着剤組成物の調製後の粘度増加が抑制され、含水率が通常あるいは低い単板を使用した場合はもとより、たとえ高含水率の単板を使用した場合であっても、合板製造時のパンク現象が抑制され、かつ、ドライアウトの問題が抑制された合板用接着剤組成物、該合板用接着剤組成物を用いる合板の製造方法、及び、該製造方法により製造された合板が提供される。 As described above, the present specification discloses various aspects. According to the embodiment disclosed in the present specification, the increase in viscosity after the preparation of the adhesive composition is suppressed, and a veneer having a high water content is used as well as a veneer having a normal or low moisture content. Even in this case, the plywood adhesive composition in which the puncture phenomenon during plywood production is suppressed and the problem of dry-out is suppressed, the method for producing plywood using the plywood adhesive composition, and the A plywood manufactured by the manufacturing method is provided.
　以下、実施例を通して本発明をさらに具体的に説明するが、本発明は以下の実施例によって限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
　［レゾール型フェノール樹脂水溶液の合成］
　フェノール６５８ｇ（７モル）と、３７％ホルムアルデヒド水溶液１１３５ｇ（ホルムアルデヒド１４モル）と、水２５０ｇとを、還流冷却装置の付いた反応器内に仕込み、攪拌しつつ、４０％水酸化ナトリウム水溶液４９０ｇ（水酸化ナトリウム４．９モル）を徐々に加え、８２℃まで昇温し、８２℃を維持しながら４時間反応させることにより、レゾール型フェノール樹脂水溶液を得た。ここに水を加えて樹脂分が４２％となるように調整した。得られたレゾール型フェノール樹脂水溶液の３０℃での粘度は、７５ｃＰ（７５ｍＰａ・ｓ）、ｐＨは１２．５であった。 [Synthesis of resol type phenol resin aqueous solution]
658 g of phenol (7 mol), 1135 g of 37% formaldehyde aqueous solution (14 mol of formaldehyde), and 250 g of water were charged into a reactor equipped with a reflux cooling apparatus and stirred, and 490 g of 40% sodium hydroxide aqueous solution (water Sodium oxide (4.9 mol) was gradually added, the temperature was raised to 82 ° C., and the mixture was allowed to react for 4 hours while maintaining 82 ° C. to obtain a resol type phenol resin aqueous solution. Water was added thereto to adjust the resin content to 42%. The obtained resol type phenol resin aqueous solution had a viscosity at 30 ° C. of 75 cP (75 mPa · s) and a pH of 12.5.
　［実施例１］
　表１に示す配合により実施例１の接着剤組成物を調製した。レゾール型フェノール樹脂としては、上記で合成したフェノール樹脂（レゾール型フェノール樹脂Ａ）を用いた。アカシア樹皮粉末としては、アカシアマンギューム樹皮の外樹皮をボールミル型粉砕機で粉砕したもの（アカシア樹皮粉末Ａ）を用いた（粒径：１０～３０μｍ、メタノール抽出分：約３０％）。炭酸カルシウムとしては、和光純薬株式会社製の試薬一級の製品（平均粒径：１μｍ）を用いた。水は、イオン交換樹脂を通過させた純水（イオン交換水）を用いた。ＰＶＡとしては、クラレ社製の「ＰＶＡ－２０５Ｓ」（ケン化度：８６．５～８９モル％）を用いた（以下例において同じ）。フェノール樹脂増量倍率（用いたフェノール樹脂の質量部に対する調製した接着剤組成物の質量部の倍率）は１．９０倍であった。 [Example 1]
The adhesive composition of Example 1 was prepared according to the formulation shown in Table 1. As the resol type phenol resin, the phenol resin synthesized above (resole type phenol resin A) was used. As the acacia bark powder, the outer bark of the acacia mangum bark was pulverized with a ball mill type pulverizer (acacia bark powder A) (particle size: 10 to 30 μm, methanol extract: about 30%). As calcium carbonate, Wako Pure Chemical Industries, Ltd., reagent grade product (average particle size: 1 μm) was used. As water, pure water (ion-exchanged water) that had been passed through an ion-exchange resin was used. As PVA, “PVA-205S” (degree of saponification: 86.5 to 89 mol%) manufactured by Kuraray Co., Ltd. was used (the same applies in the following examples). The phenol resin gain ratio (the ratio of the mass part of the prepared adhesive composition to the mass part of the phenol resin used) was 1.90 times.
　［比較例１］
　表１に示す配合により比較例１の接着剤組成物を調製した。アカシア樹皮粉末に代えてヤシガラ粉末を用いた。ＰＶＡは配合していない。水による希釈を行なっていないので、フェノール樹脂増量倍率は１．４２倍であった。 [Comparative Example 1]
An adhesive composition of Comparative Example 1 was prepared according to the formulation shown in Table 1. Coconut powder was used in place of the acacia bark powder. PVA is not blended. Since dilution with water was not performed, the phenol resin gain was 1.42 times.
　（粘度測定）
　実施例１の接着剤組成物及び比較例１の接着剤組成物について、調製直後の粘度（３０℃）、３５℃で２時間保管後の粘度（３０℃）、３５℃で４時間保管後の粘度（３０℃）を測定した。結果を表１に示す。比較例１では、粘度が経時的に急増しているのに対し、実施例１では、比較例１に比べて粘度の経時的変化（粘度増加）が少ないことが観察された。 (Viscosity measurement)
About the adhesive composition of Example 1 and the adhesive composition of Comparative Example 1, the viscosity immediately after preparation (30 ° C.), the viscosity after storage at 35 ° C. for 2 hours (30 ° C.), and after storage at 35 ° C. for 4 hours The viscosity (30 ° C.) was measured. The results are shown in Table 1. In Comparative Example 1, the viscosity increased rapidly with time, whereas in Example 1, it was observed that the change in viscosity over time (viscosity increase) was less than that in Comparative Example 1.
　（接着試験）
　実施例１の接着剤組成物及び比較例１の接着剤組成物について、単板に対する接着試験を行なった。まず、接着片として、Ｙｅｌｌｏｗ　Ｓｐｅｃｉｅｓの単板３枚（中央２．５ｍｍ厚、表裏それぞれ１．４５ｍｍ厚）を使用した。接着剤組成物の塗布量を片側２０ｇ／ｆｔ２（２１．５ｍｇ／ｃｍ２）として、調製直後の接着剤組成物を単板に塗布し、重ね合わせた。直ちに冷圧１．０ＭＰａで２５分間、その後、実施例１については、１２５℃、比較例１については、１３０℃で、熱圧１．０ＭＰａで４分間、加圧、加熱することにより、合板を作製した。 (Adhesion test)
The adhesive composition of Example 1 and the adhesive composition of Comparative Example 1 were subjected to an adhesion test on a single plate. First, three sheets of Yellow Specials (2.5 mm thickness in the center and 1.45 mm thickness in the front and back sides) were used as the adhesive pieces. The adhesive composition immediately after preparation was applied to a single plate and superposed with the application amount of the adhesive composition being 20 g / ft 2 (21.5 mg / cm 2 ) on one side. Immediately after 25 minutes at a cold pressure of 1.0 MPa, 125 ° C. for Example 1 and 130 ° C. for Comparative Example 1 at 4 ° C. for 4 minutes at a hot pressure of 1.0 MPa to heat the plywood. Produced.
　作製した合板についてＪＡＳの規格に準拠してせん断引張試験及び木部破断率（木破率）を試験した。まず、作製した合板から試験片を切り出した。試験片を２０℃の冷水中に２４時間浸漬したもの、及び、１００℃の煮沸水中に７２時間浸漬したものを、せん断引張強度試験に供した。各１０個の試験片について試験を行なった。その結果について、接着力と木部破断率の平均値を表１に示す。実施例１は比較例１に比べてフェノール樹脂増量倍率が大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、実施例１は比較例１よりも接着力及び木部破断率に優れていた。 The produced plywood was subjected to a shear tensile test and a wood breaking rate (wood breaking rate) in accordance with JAS standards. First, a test piece was cut out from the produced plywood. A specimen immersed in cold water at 20 ° C. for 24 hours and a specimen immersed in boiling water at 100 ° C. for 72 hours were subjected to a shear tensile strength test. The test was conducted on 10 test pieces each. About the result, the average value of adhesive force and a xylem breaking rate is shown in Table 1. Example 1 has a larger phenol resin weight gain than Comparative Example 1, and is advantageous in terms of environment and economy. Despite the relatively low content of phenol resin, Example 1 is more than Comparative Example 1. Was also excellent in adhesive strength and wood breaking rate.
　また、合板の接着剤層を観察したところ、実施例１及び比較例１とも、パンク現象は生じていなかった。 Further, when the adhesive layer of the plywood was observed, neither the puncture phenomenon occurred in Example 1 nor Comparative Example 1.
　実施例１に加えて追加の試験を行った。すなわち、実施例１の配合を基準として、アカシア樹皮粉末Ａの配合量のみを１～１５質量部の範囲内で種々変化させた接着剤組成物、炭酸カルシウムの配合量のみを２５～７０質量部の範囲内で種々変化させた接着剤組成物、水の配合量のみを１０～５０質量部の範囲内で種々変化させた接着剤組成物を調製し、それぞれ前記と同様に粘度測定及び接着試験を行った。また、実施例１の配合を基準として、アカシア樹皮粉末Ａの配合量のみを０質量部とした接着剤組成物を調製し、前記と同様に粘度測定及び接着試験を行った。前者の接着剤組成物（実施例群）はいずれも後者の接着剤組成物（アカシア樹皮粉末Ａを配合しなかったもの：比較例）に比べて優れる結果を示すことが確認された。また、実施例群は比較例に比べてパンク現象が抑制されていた。 In addition to Example 1, additional tests were conducted. That is, based on the formulation of Example 1, only the blending amount of the acacia bark powder A was variously changed within the range of 1 to 15 parts by mass, and only the blending amount of calcium carbonate was 25 to 70 parts by mass. The adhesive composition was changed in various ways within the above range, and the adhesive composition was changed in various amounts within the range of 10 to 50 parts by mass of water alone, and the viscosity measurement and adhesion test were performed in the same manner as described above. Went. Moreover, the adhesive composition which made only the compounding quantity of the acacia bark powder A 0 mass parts on the basis of the mixing | blending of Example 1 was prepared, and the viscosity measurement and the adhesive test were done similarly to the above. It was confirmed that all of the former adhesive compositions (Example Group) showed superior results as compared to the latter adhesive composition (without Acacia bark powder A: Comparative Example). In the example group, the puncture phenomenon was suppressed as compared with the comparative example.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［実施例２］
　表２に示す配合により実施例２の接着剤組成物を調製した。レゾール型フェノール樹脂としては、株式会社オーシカ製の「ディアノール　Ｄ－１１７」（レゾール型フェノール樹脂Ｂ、樹脂分：４３％、３０℃での粘度：１７０ｃＰ）を用いた。アカシア樹皮粉末としては、外樹皮、内樹皮を分離することなく、ボールミル型粉砕機で粉砕した、メタノール抽出分が約１７％、平均粒径が１０～５０μｍ、最大粒径が１００～１５０μｍのアカシアマンギューム樹皮粉末（アカシア樹皮粉末Ｂ）を用いた。その他の成分は、実施例１と同じものを用いた。硬化促進剤として炭酸ナトリウムを配合した。 [Example 2]
An adhesive composition of Example 2 was prepared according to the formulation shown in Table 2. As the resol type phenol resin, “Dianol D-117” (Resol type phenol resin B, resin content: 43%, viscosity at 30 ° C .: 170 cP) manufactured by Oshika Co., Ltd. was used. The acacia bark powder is acacia with a methanol extract of about 17%, an average particle size of 10-50 μm, and a maximum particle size of 100-150 μm, which is pulverized by a ball mill type grinder without separating the outer bark and inner bark. Mangum bark powder (Acacia bark powder B) was used. The other components were the same as in Example 1. Sodium carbonate was blended as a curing accelerator.
　［比較例２］
　表２に示す配合により比較例２の接着剤組成物を調製した。硬化促進剤として重炭酸ナトリウムを配合した。 [Comparative Example 2]
An adhesive composition of Comparative Example 2 was prepared according to the formulation shown in Table 2. Sodium bicarbonate was blended as a curing accelerator.
　（接着試験）
　実施例２の接着剤組成物及び比較例２の接着剤組成物について、単板に対する接着試験を行なった。まず、接着片として、ラジアータ松の単板３枚（それぞれ２．８ｍｍ厚、含水率５～６％）を使用した。接着剤組成物の塗布量を片側２０ｇ／ｆｔ２（２１．５ｍｇ／ｃｍ２）として、ドライアウト試験として、塗布後、４０℃の乾燥機中に１０分間放置し、さらに相手側単板を重ね合わせて加圧無しに１０分間放置した。その後、室温で冷圧１．０ＭＰａで２５分間、その後、１３０℃で、熱圧１．０ＭＰａで４．２分間、加圧、加熱することにより、合板を作製した。 (Adhesion test)
The adhesive composition of Example 2 and the adhesive composition of Comparative Example 2 were subjected to an adhesion test on a single plate. First, three sheets of radiata pine (each 2.8 mm thick, water content 5-6%) were used as adhesive pieces. The application amount of the adhesive composition was set to 20 g / ft 2 (21.5 mg / cm 2 ) on one side, and as a dry-out test, after application, it was left in a dryer at 40 ° C. for 10 minutes, and then the other veneer was stacked. In addition, it was left for 10 minutes without pressure. Thereafter, a plywood was produced by pressing and heating at a cold pressure of 1.0 MPa at room temperature for 25 minutes, and then at 130 ° C. and a hot pressure of 1.0 MPa for 4.2 minutes.
　作製した合板から試験片を切り出した。試験片を２０℃の冷水中に浸漬し、０．０８５ＭＰａ以上で減圧３０分、０．４５～０．４８ＭＰａで加圧３０分処理したものを、せん断引張強度試験に供した。各１０個の試験片について試験を行なった。その結果について、接着力と木部破断率の平均値を表２に示す。実施例２は比較例２に比べてフェノール樹脂増量倍率が大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、実施例２は比較例２よりも接着力に優れていた。 Specimens were cut out from the manufactured plywood. The test piece was immersed in cold water at 20 ° C. and treated at a pressure of 0.085 MPa or more for 30 minutes under reduced pressure and at a pressure of 0.45 to 0.48 MPa for 30 minutes, and then subjected to a shear tensile strength test. The test was conducted on 10 test pieces each. About the result, the average value of adhesive force and a xylem rupture rate is shown in Table 2. Example 2 has a larger phenol resin weight gain than Comparative Example 2, and is advantageous in terms of environment and economy. Despite the relatively low content of phenol resin, Example 2 is more than Comparative Example 2. Also had excellent adhesion.
　また、合板の接着剤層を観察したところ、実施例２及び比較例２とも、パンク現象は生じていなかった。 Further, when the adhesive layer of the plywood was observed, neither puncture phenomenon occurred in Example 2 and Comparative Example 2.
　実施例２に加えて追加の試験を行った。すなわち、実施例２の配合を基準として、アカシア樹皮粉末Ｂの配合量のみを１～１５質量部の範囲内で種々変化させた接着剤組成物、炭酸カルシウムの配合量のみを２５～７０質量部の範囲内で種々変化させた接着剤組成物、水の配合量のみを１０～５０質量部の範囲内で種々変化させた接着剤組成物を調製し、それぞれ前記と同様に接着試験を行った。また、実施例２の配合を基準として、アカシア樹皮粉末Ｂの配合量のみを０質量部とした接着剤組成物を調製し、前記と同様に接着試験を行った。前者の接着剤組成物（実施例群）はいずれも後者の接着剤組成物（アカシア樹皮粉末Ｂを配合しなかったもの：比較例）に比べて優れる結果を示すことが確認された。また、実施例群は比較例に比べてパンク現象が抑制されていた。 In addition to Example 2, additional tests were conducted. That is, based on the formulation of Example 2, the adhesive composition in which only the blending amount of acacia bark powder B was variously changed within the range of 1 to 15 parts by mass, and only the blending amount of calcium carbonate was 25 to 70 parts by mass. An adhesive composition with various changes within the range of 10 and an adhesive composition with various changes in the amount of water only within the range of 10 to 50 parts by mass were prepared, and an adhesion test was performed in the same manner as described above. . Moreover, the adhesive composition which made only the compounding quantity of the acacia bark powder B 0 mass parts on the basis of the mixing | blending of Example 2 was prepared, and the adhesion test was done similarly to the above. It was confirmed that all of the former adhesive compositions (Example Group) showed superior results as compared to the latter adhesive composition (without Acacia bark powder B: Comparative Example). In the example group, the puncture phenomenon was suppressed as compared with the comparative example.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　［実施例３］
　表３に示す配合により実施例３の接着剤組成物を調製した。レゾール型フェノール樹脂としては、株式会社サンベーク製の「ユーロイド　ＰＬ－２５５」（レゾール型フェノール樹脂Ｃ、樹脂分：４４％、２５℃での粘度：１５０ｃＰ）を用いた。アカシア樹皮粉末は、実施例２と同じものを用いた。その他の成分も、実施例２と同じものを用いた。 [Example 3]
An adhesive composition of Example 3 was prepared according to the formulation shown in Table 3. As the resol type phenolic resin, “Euroid PL-255” (Resol type phenolic resin C, resin content: 44%, viscosity at 25 ° C .: 150 cP) manufactured by Sunbake Co., Ltd. was used. The same acacia bark powder as in Example 2 was used. The other components were the same as in Example 2.
　［比較例３］
　表３に示す配合により比較例３の接着剤組成物を調製した。 [Comparative Example 3]
An adhesive composition of Comparative Example 3 was prepared according to the formulation shown in Table 3.
　（接着試験）
　実施例３の接着剤組成物及び比較例３の接着剤組成物について、単板に対する接着試験を、ドライアウト試験を含め、実施例２及び比較例２と同様にして行なった。ただし、接着剤組成物の塗布量を片側１７．５ｇ／ｆｔ２（１８．８ｍｇ／ｃｍ２）に減量した。結果を表３に示す。実施例３及び比較例３は実施例２及び比較例２に比べて接着剤組成物の塗布量を減量したためそれぞれ接着力が低下した。しかし、実施例３は比較例３に比べてフェノール樹脂増量倍率が大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、実施例３は比較例３と同等の接着力であった。また、実施例３は比較例３よりも木部破断率に優れていた。 (Adhesion test)
About the adhesive composition of Example 3 and the adhesive composition of Comparative Example 3, the adhesion test with respect to the veneer was performed in the same manner as in Example 2 and Comparative Example 2, including the dry-out test. However, the coating amount of the adhesive composition was reduced to 17.5 g / ft 2 (18.8 mg / cm 2 ) on one side. The results are shown in Table 3. Since Example 3 and Comparative Example 3 reduced the coating amount of the adhesive composition as compared with Example 2 and Comparative Example 2, the adhesive strength was reduced. However, Example 3 has a larger phenol resin weight gain than Comparative Example 3 and is advantageous in terms of environment and economy. Despite the relatively low content of phenol resin, Example 3 is a comparative example. The adhesive strength was equivalent to 3. In addition, Example 3 was superior to Comparative Example 3 in xylem fracture rate.
　また、合板の接着剤層を観察したところ、実施例３及び比較例３とも、パンク現象は生じていなかった。 Further, when the adhesive layer of the plywood was observed, neither puncture phenomenon occurred in Example 3 and Comparative Example 3.
　実施例３に加えて追加の試験を行った。すなわち、実施例３の配合を基準として、アカシア樹皮粉末Ｂの配合量のみを１～１５質量部の範囲内で種々変化させた接着剤組成物、炭酸カルシウムの配合量のみを２５～７０質量部の範囲内で種々変化させた接着剤組成物、水の配合量のみを１０～５０質量部の範囲内で種々変化させた接着剤組成物を調製し、それぞれ前記と同様に接着試験を行った。また、実施例３の配合を基準として、アカシア樹皮粉末Ｂの配合量のみを０質量部とした接着剤組成物を調製し、前記と同様に接着試験を行った。前者の接着剤組成物（実施例群）はいずれも後者の接着剤組成物（アカシア樹皮粉末Ｂを配合しなかったもの：比較例）に比べて優れる結果を示すことが確認された。また、実施例群は比較例に比べてパンク現象が抑制されていた。 In addition to Example 3, additional tests were conducted. That is, based on the formulation of Example 3, only the blending amount of the acacia bark powder B was variously changed within the range of 1 to 15 parts by mass, and only the blending amount of calcium carbonate was 25 to 70 parts by mass. An adhesive composition with various changes within the range of 10 and an adhesive composition with various changes in the amount of water only within the range of 10 to 50 parts by mass were prepared, and an adhesion test was performed in the same manner as described above. . Moreover, the adhesive composition which made only the compounding quantity of the acacia bark powder B 0 mass parts on the basis of the mixing | blending of Example 3 was prepared, and the adhesive test was done similarly to the above. It was confirmed that all of the former adhesive compositions (Example Group) showed superior results as compared to the latter adhesive composition (without Acacia bark powder B: Comparative Example). In the example group, the puncture phenomenon was suppressed as compared with the comparative example.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　［実施例４～６］
　表４に示す配合により実施例４～６の接着剤組成物を調製した。全成分とも、実施例１と同じものを用いた。 [Examples 4 to 6]
Adhesive compositions of Examples 4 to 6 were prepared according to the formulation shown in Table 4. All the same components as in Example 1 were used.
　（接着試験）
　実施例４～６の接着剤組成物について、単板に対する接着試験を行なった。まず、接着片として、ラジアータ松の単板３枚（それぞれ２．８ｍｍ厚、含水率７～８％）を使用した。接着剤組成物の塗布量を片側２０ｇ／ｆｔ２（２１．５ｍｇ／ｃｍ２）として、ドライアウト試験として、塗布後、４０℃の乾燥機中に１０分間放置し、さらに相手側単板を重ね合わせて加圧無しに１０分間放置した。その後、室温で冷圧１．０ＭＰａで２５分間、その後、１２５℃で、熱圧１．０ＭＰａで６分間、加圧、加熱することにより、合板を作製した。 (Adhesion test)
The adhesive compositions of Examples 4 to 6 were subjected to an adhesion test on a single plate. First, three sheets of radiata pine (each 2.8 mm thick, moisture content 7-8%) were used as adhesive pieces. The application amount of the adhesive composition was set to 20 g / ft 2 (21.5 mg / cm 2 ) on one side, and as a dry-out test, after application, it was left in a dryer at 40 ° C. for 10 minutes, and then the other veneer was stacked. In addition, it was left for 10 minutes without pressure. Thereafter, a plywood was produced by pressurizing and heating at room temperature for 25 minutes at a cold pressure of 1.0 MPa and then at 125 ° C. for 6 minutes at a hot pressure of 1.0 MPa.
　作製した合板から試験片を切り出した。試験片を２０℃の冷水中に２４時間浸漬したものを、せん断引張強度試験に供した。各１０個の試験片について試験を行なった。その結果について、接着力と木部破断率の平均値を表４に示す。実施例４～６はいずれもフェノール樹脂増量倍率が相対的に大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、接着力及び木部破断率に優れていた。特に、実施例１と比べても、概ね、接着力及び木部破断率が向上した。これは、実施例４～６は実施例１に比べて単板の樹種が異なり、かつアカシア樹皮粉末、炭酸カルシウム、水の配合量を増量したからと考えられる。 Specimens were cut out from the manufactured plywood. A test piece immersed in cold water at 20 ° C. for 24 hours was subjected to a shear tensile strength test. The test was conducted on 10 test pieces each. About the result, the average value of adhesive force and a xylem breakage rate is shown in Table 4. Examples 4 to 6 all have a relatively large phenol resin weight gain, which is advantageous in terms of environment and economy, and despite having a relatively small content of phenol resin, adhesion strength and rupture rate of xylem. It was excellent. In particular, even when compared with Example 1, the adhesive force and the xylem breaking rate were generally improved. This is presumably because Examples 4 to 6 differed from Example 1 in the type of tree of the veneer and increased amounts of acacia bark powder, calcium carbonate and water.
　また、合板の接着剤層を観察したところ、実施例４～６は、いずれもパンク現象は生じていなかった。 Further, when the adhesive layer of the plywood was observed, no puncture phenomenon occurred in any of Examples 4 to 6.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　［実施例７、８］
　表５に示す配合により実施例７、８の接着剤組成物を調製した。実施例７において、フュームドシリカとしては、日本アエロジル株式会社製の親水性フュームドシリカ「ＡＥＲＯＳＩＬ（登録商標）２００」を用いた。実施例８において、珪藻土としては、昭和化学工業株式会社製の製品を用いた。その他の成分は、実施例１と同じものを用いた。 [Examples 7 and 8]
Adhesive compositions of Examples 7 and 8 were prepared according to the formulation shown in Table 5. In Example 7, hydrophilic fumed silica “AEROSIL (registered trademark) 200” manufactured by Nippon Aerosil Co., Ltd. was used as the fumed silica. In Example 8, a product manufactured by Showa Chemical Industry Co., Ltd. was used as diatomaceous earth. The other components were the same as in Example 1.
　（接着試験）
　実施例７、８の接着剤組成物について、単板に対する接着試験を実施例４～６と同様にして行なった。結果を表５に示す。実施例７，８はいずれもフェノール樹脂増量倍率が相対的に大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、接着力及び木部破断率に優れていた。特に、実施例１と比べても、概ね、接着力及び木部破断率が向上した。フュームドシリカを配合した場合や、炭酸カルシウムと他の無機充填材とを併用した場合においても、接着力及び木部破断率が向上した。 (Adhesion test)
The adhesive compositions of Examples 7 and 8 were subjected to the adhesion test on a single plate in the same manner as in Examples 4 to 6. The results are shown in Table 5. Each of Examples 7 and 8 has a relatively large phenol resin weight gain, which is advantageous in terms of environment and economy, and despite its relatively low phenol resin content, adhesion strength and xylem rupture rate. It was excellent. In particular, even when compared with Example 1, the adhesive force and the xylem breaking rate were generally improved. Even when fumed silica was blended or when calcium carbonate and other inorganic fillers were used in combination, the adhesive force and the xylem rupture rate were improved.
　また、合板の接着剤層を観察したところ、実施例７、８は、いずれもパンク現象は生じていなかった。 Further, when the adhesive layer of the plywood was observed, in Examples 7 and 8, no puncture phenomenon occurred.
　実施例７に加えて追加の試験を行った。すなわち、実施例７の配合を基準として、アカシア樹皮粉末Ａの配合量のみを１～１５質量部の範囲内で種々変化させた接着剤組成物、炭酸カルシウムの配合量のみを２５～７０質量部の範囲内で種々変化させた接着剤組成物、水の配合量のみを１０～５０質量部の範囲内で種々変化させた接着剤組成物を調製し、それぞれ前記と同様に接着試験を行った。また、実施例７の配合を基準として、アカシア樹皮粉末Ａの配合量のみを０質量部とした接着剤組成物を調製し、前記と同様に接着試験を行った。前者の接着剤組成物（実施例群）はいずれも後者の接着剤組成物（アカシア樹皮粉末Ａを配合しなかったもの：比較例）に比べて優れる結果を示すことが確認された。また、実施例群は比較例に比べてパンク現象が抑制されていた。 In addition to Example 7, additional tests were performed. That is, based on the formulation of Example 7, the adhesive composition in which only the blending amount of acacia bark powder A was variously changed within the range of 1 to 15 parts by mass, and only the blending amount of calcium carbonate was 25 to 70 parts by mass. An adhesive composition with various changes within the range of 10 and an adhesive composition with various changes in the amount of water only within the range of 10 to 50 parts by mass were prepared, and an adhesion test was performed in the same manner as described above. . Moreover, the adhesive composition which made only the compounding quantity of the acacia bark powder A 0 mass parts on the basis of the mixing | blending of Example 7 was prepared, and the adhesion test was done similarly to the above. It was confirmed that all of the former adhesive compositions (Example Group) showed superior results as compared to the latter adhesive composition (without Acacia bark powder A: Comparative Example). In the example group, the puncture phenomenon was suppressed as compared with the comparative example.
　実施例８に加えて追加の試験を行った。すなわち、実施例８の配合を基準として、アカシア樹皮粉末Ａの配合量のみを１～１５質量部の範囲内で種々変化させた接着剤組成物、炭酸カルシウム及び珪藻土の配合量のみを２５～７０質量部の範囲内で種々変化させた接着剤組成物、水の配合量のみを１０～５０質量部の範囲内で種々変化させた接着剤組成物を調製し、それぞれ前記と同様に接着試験を行った。また、実施例８の配合を基準として、アカシア樹皮粉末Ａの配合量のみを０質量部とした接着剤組成物を調製し、前記と同様に接着試験を行った。前者の接着剤組成物（実施例群）はいずれも後者の接着剤組成物（アカシア樹皮粉末Ａを配合しなかったもの：比較例）に比べて優れる結果を示すことが確認された。また、実施例群は比較例に比べてパンク現象が抑制されていた。 In addition to Example 8, additional tests were performed. That is, with reference to the formulation of Example 8, only the blending amount of the acacia bark powder A was varied in the range of 1 to 15 parts by mass, and only the blending amounts of calcium carbonate and diatomaceous earth were 25 to 70. Prepare adhesive compositions with various changes within the range of parts by mass, and adhesive compositions with various amounts of water only within the range of 10 to 50 parts by mass. went. Moreover, the adhesive composition which made only the compounding quantity of the acacia bark powder A 0 mass parts on the basis of the mixing | blending of Example 8 was prepared, and the adhesion test was done similarly to the above. It was confirmed that all of the former adhesive compositions (Example Group) showed superior results as compared to the latter adhesive composition (without Acacia bark powder A: Comparative Example). In the example group, the puncture phenomenon was suppressed as compared with the comparative example.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　［実施例９、１０］
　表６に示す配合により実施例９、１０の接着剤組成物を調製した。レゾール型フェノール樹脂としては、冒頭で説明した合成法と同じ条件で合成したレゾール型フェノール樹脂Ｄ（３０℃での粘度８２ｃＰ（８２ｍＰａ・ｓ）、ｐＨ１２．５）を用いた。その他の配合成分は、実施例１と同じものを用いた。 [Examples 9 and 10]
Adhesive compositions of Examples 9 and 10 were prepared according to the formulation shown in Table 6. As the resol-type phenol resin, a resol-type phenol resin D (viscosity at 30 ° C. (82 cP (82 mPa · s), pH 12.5)) synthesized under the same conditions as in the synthesis method described at the beginning was used. The other ingredients were the same as in Example 1.
　（パンク試験）
　実施例９、１０の接着剤組成物について、合板熱圧時に起こるパンク現象を想定した試験を行った。まず、接着片として、高周波木材水分計値で１２％、１５％、１６．５％に調整したラジアータ松の単板３枚（それぞれ２．８ｍｍ厚）を使用した。接着剤組成物の塗布量を片側１７ｇ／ｆｔ２（１８．８ｍｇ／ｃｍ２）として、調製直後の接着剤組成物を単板に塗布し、重ね合わせた。直ちに、冷圧１．０ＭＰａで３０分間、その後、１３０℃で、熱圧１．０ＰＭａで７分間、加圧、加熱し、解圧時パンクが発生するか否かを確認した。パンクの非発生率を下記式により算出した。各実施例において、１０個の試験体で試験を行った。結果を表６に示す。 (Punk test)
About the adhesive composition of Example 9, 10, the test which assumed the puncture phenomenon which occurs at the time of plywood hot press was done. First, three pieces of Radiata pine single plates (2.8 mm thick each) adjusted to 12%, 15% and 16.5% with high-frequency wood moisture meter values were used as adhesive pieces. The adhesive composition immediately after preparation was applied to a veneer and superposed, with the application amount of the adhesive composition being 17 g / ft 2 (18.8 mg / cm 2 ) on one side. Immediately, it was pressurized and heated at a cold pressure of 1.0 MPa for 30 minutes, and then at 130 ° C. and a hot pressure of 1.0 PMa for 7 minutes, and it was confirmed whether puncture occurred during decompression. The non-occurrence rate of puncture was calculated by the following formula. In each example, the test was performed with 10 specimens. The results are shown in Table 6.
　パンク非発生率＝（パンクが発生しなかった試験体の数／全試験体の数）×１００ Puncture non-occurrence rate = (number of specimens in which puncture did not occur / number of all specimens) × 100
　実施例１０は、実施例９と比べて、パンクの非発生率が高かった。すなわち、良好な結果であった。これは、実施例１０の接着剤組成物は、実施例９の接着剤組成物に比べて、糊液中に含まれる水分量が少なかったためと考えられる。 Example 10 had a higher non-occurrence of puncture than Example 9. That is, it was a favorable result. This is probably because the adhesive composition of Example 10 contained less water than the adhesive composition of Example 9.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　［実施例１１～１４］
　表７に示す配合により実施例１１～１４の接着剤組成物を調製した。レゾール型フェノール樹脂としては、実施例９、１０と同じもの（３０℃での粘度９０ｃＰ（９０ｍＰａ・ｓ）、ｐＨ１２．５）を用いた。その他の配合成分も、実施例９、１０と同じものを用いた。 [Examples 11 to 14]
Adhesive compositions of Examples 11 to 14 were prepared according to the formulation shown in Table 7. As the resol type phenol resin, the same resin as in Examples 9 and 10 (viscosity at 30 ° C. (90 mPa · s), pH 12.5) was used. The other compounding components were the same as in Examples 9 and 10.
　（パンク試験）
　実施例１１～１４の接着剤組成物について、合板熱圧時に起こるパンク現象を想定した試験を行った。まず、接着片として、高周波木材水分計値で１３．５％に調整した南洋材の単板５枚（中央３．７ｍｍ厚、表裏それぞれ０．８ｍｍ厚）を使用した。接着剤組成物の塗布量を片側１７ｇ／ｆｔ２（１８．８ｍｇ／ｃｍ２）として、調製直後の接着剤組成物を単板に塗布し、重ね合わせた。直ちに冷圧１．０ＭＰａで３０分間、その後、１２５℃で、熱圧１．０ＭＰａで１０分５０秒間、加圧、加熱し、解圧時パンクが発生するか否かを確認した。パンクの非発生率を実施例９、１０と同様の式により算出した。各実施例において、１０個の試験体で試験を行った。結果を表７に示す。 (Punk test)
The adhesive compositions of Examples 11 to 14 were tested assuming a puncture phenomenon that occurred during hot pressing of plywood. First, as the adhesive pieces, five single plates of south sea wood (3.7 mm thick at the center and 0.8 mm thick each on the front and back sides) adjusted to 13.5% with a high-frequency wood moisture meter value were used. The adhesive composition immediately after preparation was applied to a veneer and superposed, with the application amount of the adhesive composition being 17 g / ft 2 (18.8 mg / cm 2 ) on one side. Immediately, the pressure was increased by heating at a cold pressure of 1.0 MPa for 30 minutes, and then at 125 ° C. and a hot pressure of 1.0 MPa for 10 minutes 50 seconds, and it was confirmed whether or not puncture occurred during decompression. The non-occurrence rate of puncture was calculated by the same formula as in Examples 9 and 10. In each example, the test was performed with 10 specimens. The results are shown in Table 7.
　アカシア樹皮粉末の配合量が増えるに従いパンク非発生率が増加することが明らかになった。 It became clear that the puncture-free rate increased as the blending amount of Acacia bark powder increased.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　［実施例１５～１８］
　表８に示す配合により実施例１５～１８の接着剤組成物を調製した。レゾール型フェノール樹脂としては、冒頭で説明した合成法と同じ条件で合成したレゾール型フェノール樹脂Ｅ（３０℃での粘度８０ｃＰ（８０ｍＰａ・ｓ）、ｐＨ１２．５）を用いた。その他の配合成分は、実施例１と同じものを用いた。 [Examples 15 to 18]
Adhesive compositions of Examples 15 to 18 were prepared according to the formulation shown in Table 8. As the resol-type phenol resin, a resol-type phenol resin E (viscosity at 30 ° C., 80 cP (80 mPa · s), pH 12.5) synthesized under the same conditions as the synthesis method described at the beginning was used. The other ingredients were the same as in Example 1.
　（パンク試験）
　実施例１５～１８の各接着剤組成物について、合板熱圧時に起こるパンク現象を想定した試験を行った。まず、接着片として、高周波木材水分計値で１６．５％に調整した南洋材の単板５枚（中央３．７ｍｍ厚、表裏それぞれ０．８ｍｍ厚）を使用した。接着剤組成物の塗布量を片側１７ｇ／ｆｔ２（１８．８ｍｇ／ｃｍ２）として、調製直後の接着剤組成物を単板に塗布し、重ね合わせた。直ちに冷圧１．０ＭＰａで３０分間、その後、１３０℃で、熱圧１．０ＭＰａで１０分５０秒間、加圧、加熱し、解圧時パンクが発生するか否かを確認した。パンクの非発生率を実施例９、１０と同様の式によって算出した。各実施例において、１０個の試験体で試験を行った。結果を表８に示す。 (Punk test)
Each adhesive composition of Examples 15 to 18 was subjected to a test assuming a puncture phenomenon that occurred during hot pressing of plywood. First, as the adhesive pieces, five single plates of southern sea wood (3.7 mm thick at the center and 0.8 mm thick each on the front and back sides) adjusted to 16.5% with a high-frequency wood moisture meter value were used. The adhesive composition immediately after preparation was applied to a veneer and superposed, with the application amount of the adhesive composition being 17 g / ft 2 (18.8 mg / cm 2 ) on one side. Immediately, the pressure was increased by heating at a cold pressure of 1.0 MPa for 30 minutes, and then at 130 ° C. and a hot pressure of 1.0 MPa for 10 minutes and 50 seconds, and it was confirmed whether or not puncture occurred during decompression. The non-occurrence rate of puncture was calculated by the same formula as in Examples 9 and 10. In each example, the test was performed with 10 specimens. The results are shown in Table 8.
　（接着試験）
　実施例１５～１８の各接着剤組成物について、単板に対する接着試験を行なった。まず、接着片として、高周波木材水分計値で８％に調整した南洋材の単板５枚（中央３．７ｍｍ厚、表裏それぞれ１．２ｍｍ厚）を使用した。接着剤組成物の塗布量を片側１７ｇ／ｆｔ２（１８．８ｍｇ／ｃｍ２）として、調製直後の接着剤組成物を単板に塗布し、重ね合わせた。直ちに冷圧１．０ＭＰａで３０分間、その後、１３０℃で、熱圧１．０ＭＰａで１０分５０秒間、加圧、加熱することにより、合板を作製した。 (Adhesion test)
Each adhesive composition of Examples 15 to 18 was subjected to an adhesion test on a single plate. First, as a piece of adhesive, 5 single plates of South Sea wood (3.7 mm thick at the center and 1.2 mm thick each on the front and back sides) adjusted to 8% with a high-frequency wood moisture meter value were used. The adhesive composition immediately after preparation was applied to a veneer and superposed, with the application amount of the adhesive composition being 17 g / ft 2 (18.8 mg / cm 2 ) on one side. A plywood was produced by immediately pressing and heating at a cold pressure of 1.0 MPa for 30 minutes, and then at 130 ° C. and a hot pressure of 1.0 MPa for 10 minutes and 50 seconds.
　作製した合板についてＪＡＳ規格に準拠してせん断引張試験及び木部破断率（木破率）を試験した。まず、作製した合板から試験片を切り出した。試験片を１００℃の煮沸水中に７２時間浸漬したものを、せん断引張強度試験に供した。各１０個の試験片について試験を行なった。その結果について、接着力と木部破断率の平均値を表８に示す。 The produced plywood was tested for shear tensile test and wood part breaking rate (wood breaking rate) in accordance with JAS standards. First, a test piece was cut out from the produced plywood. A test piece immersed in boiling water at 100 ° C. for 72 hours was subjected to a shear tensile strength test. The test was conducted on 10 test pieces each. About the result, the average value of adhesive force and a xylem rupture rate is shown in Table 8.
　実施例１６は実施例１５に比べてパンク非発生率が高く、実施例１８は実施例１６に比べてパンク非発生率がさらに高く、また、実施例１７も実施例１６に比べてパンク非発生率が高かった。これは、実施例１６は実施例１５に比べて糊液中に含まれる水分量が少なく、実施例１８は実施例１６に比べて糊液中に含まれる水分量がさらに少なく、また、実施例１７は実施例１６に比べて糊液中に含まれるアカシア樹皮粉末の量が多かったためと考えられる。 Example 16 has a higher puncture-free rate than Example 15, Example 18 has a higher puncture-free rate than Example 16, and Example 17 also has no puncture compared to Example 16. The rate was high. In Example 16, the amount of water contained in the paste liquid is smaller than that in Example 15, and in Example 18, the amount of water contained in the paste liquid is smaller than that in Example 16. No. 17 is considered to be because the amount of acacia bark powder contained in the paste liquid was larger than that in Example 16.
　実施例１５～１８は、いずれもフェノール樹脂の増量倍率が相対的に大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、接着力及び木部破断率に優れていた。 Examples 15 to 18 all have a relatively large phenol resin gain ratio, which is advantageous in terms of environmental friendliness and economy, and despite having a relatively low phenol resin content, adhesion strength and xylem. Excellent breaking rate.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　［実施例１９］
　表９に示す配合により実施例１９の接着剤組成物を調製した。レゾール型フェノール樹脂としては、実施例２と同様の、株式会社オーシカ製の「ディアノール　Ｄ－１１７」（レゾール型フェノール樹脂Ｂ、樹脂分：４３％、３０℃での粘度：２００ｃＰ）を用いた。その他の配合成分は、実施例１と同じものを用いた。 [Example 19]
An adhesive composition of Example 19 was prepared according to the formulation shown in Table 9. As the resol type phenolic resin, “Dianol D-117” (Resol type phenolic resin B, resin content: 43%, viscosity at 30 ° C .: 200 cP) manufactured by Oshika Co., Ltd. was used as in Example 2. . The other ingredients were the same as in Example 1.
　（接着試験）
　実施例１９の接着剤組成物について、単板に対する接着試験を実施例１５～１８と同様にして行なった。まず、接着片として、高周波木材水分計値で８％に調整した南洋材の単板５枚を使用して、合板を作製した。 (Adhesion test)
With respect to the adhesive composition of Example 19, an adhesion test for a single plate was conducted in the same manner as in Examples 15-18. First, plywood was produced using five single plates of South Sea wood adjusted to 8% with high-frequency wood moisture meter values as adhesive pieces.
　作製した合板についてＪＡＳ規格に準拠してせん断引張試験及び木部破断率（木破率）を試験した。まず、作製した合板から試験片を切り出した。試験片を１００℃の煮沸水中に７２時間浸漬したものを、せん断引張強度試験に供した。各１０個の試験片について試験を行なった。その結果について、接着力と木部破断率の平均値を表９に示す。 The produced plywood was tested for shear tensile test and wood part breaking rate (wood breaking rate) in accordance with JAS standards. First, a test piece was cut out from the produced plywood. A test piece immersed in boiling water at 100 ° C. for 72 hours was subjected to a shear tensile strength test. The test was conducted on 10 test pieces each. Table 9 shows the average values of the adhesive strength and the xylem rupture rate for the results.
　実施例１９は、フェノール樹脂の増量倍率が大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、接着力及び木部破断率に優れていた。炭酸カルシウム増量のためと考えられるが、接着性能は高く、合板の接着剤層を観察したところ、パンク現象(剥離)は生じていなかった。 Example 19 had a large phenol resin gain ratio and was advantageous in terms of environment and economy, and was excellent in adhesive strength and xylem rupture rate despite its relatively low phenol resin content. Although it is thought to be due to the increase in calcium carbonate, the adhesive performance was high, and when the adhesive layer of the plywood was observed, the puncture phenomenon (peeling) did not occur.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　［実施例２０］
　表１０に示す配合により実施例２０の接着剤組成物を調製した。レゾール型フェノール樹脂としては、実施例９、１０と同じもの（３０℃での粘度１００ｃＰ（１００ｍＰａ・ｓ）、ｐＨ１２．５）を用いた。その他の配合成分は、実施例１と同じものを用いた。 [Example 20]
An adhesive composition of Example 20 was prepared according to the formulation shown in Table 10. As the resol-type phenol resin, the same resin as in Examples 9 and 10 (viscosity at 30 ° C. 100 cP (100 mPa · s), pH 12.5) was used. The other ingredients were the same as in Example 1.
　（接着試験）
　実施例２０の接着剤組成物について、単板に対する接着試験を実施例１９と同様にして行なった。ただし、接着片としては、高周波木材水分計値で１６．５％に調整した南洋材の単板５枚を使用した。接着力と木部破断率の平均値を表１０に示す。 (Adhesion test)
About the adhesive composition of Example 20, the adhesion test with respect to the veneer was conducted in the same manner as in Example 19. However, as the adhesive piece, five single plates of South Sea wood adjusted to 16.5% with the high-frequency wood moisture meter value were used. Table 10 shows the average values of the adhesive strength and the rupture rate of the xylem.
　実施例２０は、フェノール樹脂の増量倍率が比較的大きく、環境性、経済性に有利であり、フェノール樹脂の含有量が相対的に少ないにも拘らず、接着力及び木部破断率に優れていた。また、合板の接着剤層を観察したところ、パンク現象（剥離）は生じていなかった。 Example 20 has a relatively large weight gain of phenolic resin, which is advantageous in terms of environment and economy, and is excellent in adhesive strength and xylem rupture rate despite the relatively low content of phenolic resin. It was. Moreover, when the adhesive layer of the plywood was observed, no puncture phenomenon (peeling) occurred.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　以上、本発明の実施形態及び実施例が詳細に説明されたが、上記した説明は、全ての局面において例示であって、本発明はこれらに限定されない。例示されていない無数の変形例が、本発明の範囲から外れることなく想定され得ると解釈される。本発明を表現するために、上述において、実施形態及び実施例を通して、本発明を適切かつ十分に説明した。しかし、当業者であれば、上述の実施形態及び実施例を変更及び／又は改良することは容易になし得ることであると認識すべきである。したがって、当業者が実施する変更形態又は改良形態が、請求の範囲に記載された請求項の権利範囲を離脱するレベルのものでない限り、当該変更形態又は当該改良形態は、当該請求項の権利範囲に包括されると解釈される。 As mentioned above, although embodiment and the Example of this invention were described in detail, above-described description is an illustration in all the aspects, Comprising: This invention is not limited to these. It is construed that countless variations that are not illustrated can be envisaged without departing from the scope of the present invention. In order to express the present invention, the present invention has been described above appropriately and adequately through the embodiments and examples. However, it should be recognized by those skilled in the art that changes and / or improvements to the above-described embodiments and examples can be readily made. Therefore, unless the modifications or improvements implemented by those skilled in the art are at a level that departs from the scope of the claims recited in the claims, the modifications or improvements are not limited to the scope of the claims. To be construed as inclusive.
　本発明は、合板用接着剤組成物、合板の製造方法及び合板の技術分野において、広範な産業上の利用可能性を有する。 The present invention has wide industrial applicability in the technical field of plywood adhesive composition, plywood manufacturing method and plywood.

Claims (9)

  1. 　樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～５０質量部とが添加されることにより調製されたことを特徴とする合板用接着剤組成物。 1 to 15 parts by weight of acacia bark powder, 25 to 70 parts by weight of an inorganic filler, and 10 to 50 parts by weight of water are added to 100 parts by weight of an aqueous resol type phenolic resin having a resin content of 40 to 50% by weight. An adhesive composition for plywood, which is prepared by
  2. 　樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１０質量部と、無機充填材２５～５０質量部と、水２５～５０質量部とが添加されることにより調製されたことを特徴とする合板用接着剤組成物。 1 to 10 parts by weight of an acacia bark powder, 25 to 50 parts by weight of an inorganic filler, and 25 to 50 parts by weight of water are added to 100 parts by weight of an aqueous resol type phenolic resin having a resin content of 40 to 50% by weight. An adhesive composition for plywood, which is prepared by
  3. 　樹脂分が４０～５０質量％のレゾール型フェノール樹脂水溶液１００質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部と、水１０～２５質量部とが添加されることにより調製されたことを特徴とする合板用接着剤組成物。 1 to 15 parts by weight of acacia bark powder, 25 to 70 parts by weight of an inorganic filler, and 10 to 25 parts by weight of water are added to 100 parts by weight of an aqueous resol type phenolic resin having a resin content of 40 to 50% by weight. An adhesive composition for plywood, which is prepared by
  4. 　アカシア樹皮粉末は、平均粒径が１０～１５０μｍであることを特徴とする請求項１から３のいずれか１項に記載の合板用接着剤組成物。 The adhesive composition for plywood according to any one of claims 1 to 3, wherein the acacia bark powder has an average particle size of 10 to 150 µm.
  5. 　ポリビニルアルコール０．１～３質量部がさらに添加されていることを特徴とする請求項１から４のいずれか１項に記載の合板用接着剤組成物。 The adhesive composition for plywood according to any one of claims 1 to 4, further comprising 0.1 to 3 parts by mass of polyvinyl alcohol.
  6. 　フュームドシリカ０．１～２質量部がさらに添加されていることを特徴とする請求項１から５のいずれか１項に記載の合板用接着剤組成物。 The adhesive composition for plywood according to any one of claims 1 to 5, wherein 0.1 to 2 parts by mass of fumed silica is further added.
  7. 　請求項１から６のいずれか１項に記載の合板用接着剤組成物を単板に塗布し、複数の単板を重ね合わせ、加圧、加熱することを特徴とする合板の製造方法。 A method for producing plywood, comprising applying the adhesive composition for plywood according to any one of claims 1 to 6 to a single plate, stacking a plurality of single plates, pressurizing and heating.
  8. 　請求項７に記載の製造方法により製造されたことを特徴とする合板。 A plywood manufactured by the manufacturing method according to claim 7.
  9. 　接着剤層が、硬化したフェノール樹脂４０～５０質量部に対し、アカシア樹皮粉末１～１５質量部と、無機充填材２５～７０質量部とを含むことを特徴とする合板。 A plywood characterized in that the adhesive layer contains 1 to 15 parts by mass of acacia bark powder and 25 to 70 parts by mass of an inorganic filler with respect to 40 to 50 parts by mass of the cured phenol resin.
PCT/JP2011/002482 2010-05-06 2011-04-27 Adhesive composition for plywood, method for producing plywood, and plywood WO2011138858A1 (en)

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CN106584610A (en) * 2016-12-21 2017-04-26 陈永钦 Special glue regulating agent for plywood industry
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CN103361013B (en) * 2013-08-08 2014-07-23 周广胜 Composite phenolic glue composition and application method thereof
CN103773296A (en) * 2013-12-25 2014-05-07 广西宾阳县荣良新材料科技有限公司 Glue composition for plywood
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EP3617286A4 (en) * 2017-04-25 2021-01-06 Wood One Co., Ltd. Adhesive
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TW201207064A (en) 2012-02-16

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