WO2006102809A1 - Procede pour l’application d’adhesif polymere en tant qu’agent adhesif pour coller du bois ou une garniture - Google Patents

Procede pour l’application d’adhesif polymere en tant qu’agent adhesif pour coller du bois ou une garniture Download PDF

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Publication number
WO2006102809A1
WO2006102809A1 PCT/CN2005/001957 CN2005001957W WO2006102809A1 WO 2006102809 A1 WO2006102809 A1 WO 2006102809A1 CN 2005001957 W CN2005001957 W CN 2005001957W WO 2006102809 A1 WO2006102809 A1 WO 2006102809A1
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Prior art keywords
starch
polymeric
adhesive
modified
wood
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PCT/CN2005/001957
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English (en)
French (fr)
Inventor
Shouhui Zhu
Original Assignee
Shouhui Zhu
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Publication date
Application filed by Shouhui Zhu filed Critical Shouhui Zhu
Priority to JP2008503349A priority Critical patent/JP2008534717A/ja
Priority to US11/887,694 priority patent/US20100024977A1/en
Publication of WO2006102809A1 publication Critical patent/WO2006102809A1/zh

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Classifications

    • 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
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/04—Starch derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
    • 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
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate

Definitions

  • the present invention pertains to industrial adhesives, and more particularly to a method of bonding wood products using a starch and a polymeric polymeric material as an adhesive.
  • the glue made of starch is usually only used for bonding products such as paper products, and the bonding strength is not high, and it is difficult to adhere to products requiring high bonding strength, such as in furniture production. Bonding and fixing between wooden products.
  • An object of the present invention is to provide a method for bonding wood products using starch and a polymeric polymer material as an adhesive in view of the disadvantages of the prior art, and the method can improve the bonding strength of wood products.
  • the invention provides a method for bonding wood products or decorations by using a polymeric binder as a binder, and the components of the polymer binder include starch and a polymer material and a binder containing the polymer material, and the adhesive is made.
  • the method of the mixture comprises the steps of: modifying the starch and modifying the polymeric polymer raw material; and placing the modified starch and the modified polymeric polymer at a temperature of 20°-100° C; Graft polymerization is carried out in a container having a temperature of 45° - 65° C to form a polymeric binder, and the starch modification step further comprises the following steps:
  • Oxidative modification of starch The purpose of oxidation is to oxidize a part of the hydroxyl group (0H) on the starch molecule to an aldehyde group and a carboxyl group (C00H), which can be selected on the group of C 2 - C 6 carbon atoms.
  • the oxidation is carried out in an aqueous solution of an alkaline starch having a pH of 6 to 14.
  • Starch etherification modification is a starch derivative formed by a hydroxyl group in a starch molecule and a hydroxyl group in a hydroxy compound through an oxygen atom; an etherification modified modifier is added as an acid Type or epoxy chlorpromide; at 30 ° -90 ° C; optimum temperature 50 ° -65 ° C in the solution of acid or epoxy chlorpromide and starch to form etherified starch derivatives, acid Or the amount of epichlorohydrin added is 1-15%, which not only increases the viscosity and toughness, but also has a certain anti-corrosion function, increasing the water resistance and the bonding strength;
  • the modification of the polymeric polymer further comprises the following steps: emulsifying copolymerization of dissolved PVA (polyethylene glycol) or PVAC (polyvinyl acetate), emulsion copolymerization method: cooling the dissolved PVA or PVAC solution to 50. C -120 V , the optimum temperature is 60 ° -80 ° C
  • emulsifier, initiator and appropriate amount of VAC (ethylene acetate) or PA (polyacrylic acid sodium) or other polymer materials for emulsion polymerization make the close connection
  • the PVA colloid forms a dispersed latex particle that reduces viscosity and increases fluidity.
  • the amount of the initiator is determined to be 1 -15 %, and the amount of VAC is 3 -15 %; the graft polymerization step of the modified starch and the polymerized polymer further includes the following Step: Grafting the modified starch with the modified polymeric polymer and the binder containing the polymeric polymer in a container of 20 "C-100 , optimal temperature 50 ° -65 ° C Polymerize and interact to produce the best performance natural vegetable starch binder.
  • the adhesive can stick to all kinds of products made of wood material; the product adhered with the glue of the invention can be immersed in water for 48 hours without cracking, at 63 ° C The water is boiled for 3 hours without cracking.
  • the standard specimen has a shear strength of 5-14mpa and a wet strength of 2-7mpa.
  • the above wood products are one of the following products: wooden furniture, cloth furniture, kitchen furniture, plywood, MDF, particle board, blockboard;
  • the above binder can also be used in the correction fluid.
  • the method of the present invention can adhere to all wood products, such as wooden furniture, cloth furniture, kitchen furniture, plywood, blockboard, MDF, particle board, and the product adhered by the glue of the invention can be used. Soaking water for 48 hours without cracking, boiling in 63 °C water for 3 hours without cracking, the standard sample shear strength can reach 5-14mpa, the wet strength reaches 2-7mpa, and can also be used as the interior wall paint, the putty foundation Glue, can be used for interior wall tiles, wallpapers, wall coverings, decorative stickers, carpets and leather adhesives.
  • the invention provides a method for bonding wood products or decorations by using a polymeric binder as an adhesive.
  • the method of polymerizing a binder comprises a starch and a polymeric polymer material and a binder containing the polymer polymeric material, and the method for preparing the binder comprises the following steps: modifying the starch and modifying the polymerized polymer raw material
  • the modified starch and the modified polymeric polymer and the binder containing the polymeric material are placed in a container having a temperature of 20 ° C - 100 ° C and an optimum temperature of 45 ° - 65 ° C.
  • the graft polymerization is carried out to prepare a polymeric binder, and the starch modification step can be carried out by a three-stage modification step:
  • Modification by one step or two steps or three steps of the following three-stage modification step may be determined according to the purpose or occasion of the use of the binder, and one or more steps may be used for modification.
  • the bonding strength is not high, it can be modified by only one step or two steps.
  • three steps can be used for modification.
  • the order can be changed.
  • the specific operation procedure of the three-stage modification step is described below: The principle of the third-stage modification is based on the group of different chemical reactions on the Ci-C 6 carbon atom in the starch molecule, and the C 2 is determined.
  • the hydroxyl groups on C 3 and C 6 have chemical reaction ability, which is an intrinsic factor for the modification of starch macromolecules.
  • Oxidative modification of starch The purpose of oxidation is to oxidize a part of the hydroxyl group ( 0H ) on the starch molecule to an aldehyde group and a carboxyl group (C00H ), which is selective on a group of Ci-C 6 carbon atoms.
  • the oxidation is carried out in an aqueous alkaline starch solution having a pH of 6 to 14.
  • the amount of the oxidizing agent is 0.8 - 10%, and the temperature of the aqueous alkaline starch solution is 30 ° - 100 ° C, and the optimum temperature is 40 ° - 55 ° C, the aldehyde group has anti-corrosion function, and the carboxyl group has the function of enhancing the adhesion to the wood fiber; (2) .
  • Gelatinization modification of starch carried out in an alkaline aqueous solution, the gelatinization is to continue to modify the remaining hydroxyl groups in the starch molecule on the basis of oxidation; the modification method is to continuously add an appropriate amount of alkali solution, so that The hydroxyl group (0H) in the starch molecule becomes starch nano (st _0Na), and the glue in the reaction system is thickened and thickened, and the viscosity is also increased; the amount of the alkaline solution water is determined to be 1 to 15%. Or the enthalpy value is 7-20, the temperature of the alkaline starch aqueous solution is 30 ° C - 100 ° C, and the optimum temperature is 50 ° -65. Go
  • Starch etherification modification is a starch derivative formed by a hydroxyl group in a starch molecule and a hydroxyl group in a hydroxy compound through an oxygen atom; an etherification modified modifier is added as an acid Or an oxiranoid; an acid or epichlorohydrin reacts with starch at 30 ° C - 100 ° C, at an optimum temperature of 50 ° -65 ° C to form an etherified starch derivative, acid Or the amount of epichlorohydrin added is 1-15%, which not only increases the viscosity and toughness, but also has a certain anti-corrosion function, increasing the water resistance and the bonding strength;
  • Cross-linking modification Adding an appropriate amount of urea to the glue can crosslink the starch molecules.
  • the optimum temperature is 50°-65° C, urea and
  • the aldehyde group in the starch molecule or the aldehyde group generated during the oxidation process condenses to form a certain high polymer, and the amount of urea added is 1 to 10%, which plays a certain auxiliary role for the viscosity and strength of the glue;
  • the modification of the polymeric polymer further comprises the following steps: emulsifying copolymerization of dissolved PVA (polyethyl alcohol) or PVAC (polyvinyl acetate), emulsion copolymerization method: cooling the dissolved PVA or PVAC solution to 50 V -100 °C, the optimum temperature is 65 ° -85 ° C, adding emulsifier, initiator and the most suitable VAC (ethylene acetate) or PA (polyacrylic acid sodium) for emulsion polymerization, making the closely related PVA
  • the colloid forms a dispersed latex particle which reduces viscosity and increases fluidity.
  • the amount of initiator is determined to be 1 -15 %, and the amount of VAC is 3 -15 %;
  • the graft polymerization step of the modified starch and the polymerized polymer further includes the following Step:
  • the modified starch and the modified polymeric polymer are grafted and polymerized in a container at 20 ° C - 100 ° C and an optimum temperature of 45 ° -65 ° C to produce the most performance.
  • Excellent natural plant starch glue
  • the procedure for bonding the above prepared adhesive to the wood product is as follows - at -10 -50 .
  • the adhesive can be used at a temperature of -10 to 50 ° C. It can be dried at 5 to 25 minutes at room temperature, cured within 24 hours, and the standard sample can be applied with a pressure of 5 kg or more.
  • Various products made of wood materials such as wooden furniture, fabric furniture, kitchen furniture, plywood, blockboard, MDF, particleboard, products adhered with the glue of the invention can be immersed in water for 48 hours without cracking, at 63 °C
  • It can be used for interior wall paint, paint and interior wall putty adhesive, and can be used for interior wall magnetics. It can be used for interior wall paint, paint and interior wall putty. It can be used for interior wall paint, paint and interior wall putty. Brick, wallpaper, decorative stickers, wall coverings, carpets and leather binders.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Veneer Processing And Manufacture Of Plywood (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Description

一种应用聚合粘合剂作为粘接剂粘接木质品或装饰品的方法
技术领域
本发明属于工业粘合剂， 尤其是一种应用淀粉和聚合高分子材料作为 粘合剂粘接木质品的方法。
背景技术
在现有技术中， 采用淀粉制作的胶合剂通常只用于粘结纸质品之类的 制品， 粘贴强度不高， 很难粘贴住需要粘贴强度要求较高的产品， 如在家 具制作中的木质产品间的粘结固接。
发明内容
本发明的目的在于针对已有技术所存在的缺点， 提供一种应用淀粉和 聚合高分子材料作为粘合剂粘接木质品的方法， 采用本方法可提高木质产 品的粘接强度。
本发明提供一种应用聚合粘合剂作为粘合剂粘接木质品或装饰品的方 法， 聚合胶合剂的成分包括淀粉和聚合高分子材料及其含有高分子聚合材 料的粘合剂， 制作粘合剂的方法包括如下步骤： 将淀粉进行改性、 将聚合 高分子原料进行改性； 将改性后的淀粉和改性后的聚合高分子放置在温度 为 20° -100° C; 最佳温度为 45° -65° C的容器中进行接枝聚合制成聚合 胶合剂， 淀粉改性步骤进一步包括如下步骤：
(一）. 淀粉的氧化改性：氧化的目的是将淀粉分子上的部分羟基（ 0H ) 氧化为醛基及羧基（C00H ), 可在 C2— C6碳原子上的基团上有选择性的 进行氧化， 氧化是在 PH值为 6-14的碱性淀粉水溶液中氧化， 氧化剂的用 量为 0. 8 - 10 % , 碱性溶液水温度为 30° -100° C, 最佳温度为 45° -55 ° C; 醛基具有防腐功能， 羧基对木质纤维具有增强粘接力的功能；
(二) . 淀粉的糊化改性： 在碱性水溶液中进行， 糊化是在氧化的基础 上继续对淀粉分子中的剩余羟基进行改性； 改性方法是不断加入适量的碱 溶液， 使淀粉分子中的羟基 （0H ) 变成淀粉纳（st _0Na) , 这时反应系统 中的胶液则由稀变浓， 粘度也随之增高； 碱性溶液水的添加量确定为 1 一 15 %； 或 TO值为 7-20。
(三) . 淀粉的醚化改性： 是在淀粉分子中的某羟基与羟基化合物中的 一个羟基通过氧原子的联结形成另外一种淀粉衍生物； 添加醚化改性的改 性剂为酸类或环氧氯丙垸类；在 30° -90° C; 最佳温度为 50° -65° C的胶 液中酸或环氧氯丙垸类与淀粉反应形成醚化淀粉衍生物， 酸或环氧氯丙烷 类的添加量为 1-15 % , 既增加粘性和韧性， 又具有一定的防腐功能， 增加 耐水性及胶接强度；
(四） 交联改性： 在胶液中加适量的尿素对淀粉分子可起交联作用， 在 40° -85° C,最佳温度为 50° -65° C的胶液中，尿素与淀粉分子中的醛 基或氧化过程中产生的醛基起缩合作用， 形成某种高聚物， 尿素的添加量 为 1 一 10 %， 对胶液的粘度与强度起一定辅助作用；
所述的聚合高分子的改性进一步包括如下步骤： 将溶解的 PVA (聚乙 稀醇）或 PVAC (聚醋酸乙烯)乳化共聚改性，乳化共聚法：是将溶解的 PVA 或 PVAC溶液降温至 50 。C -120 V ， 最佳温度为 60° -80° C加入乳化剂、 引发剂及适量的 VAC (乙酸乙稀）或 PA (聚丙烯酸纳） 或其它高分子材料 进行乳化聚合， 使紧密相联的 PVA胶体形成分散型的乳胶粒， 降低粘度增 加流动性。 引发剂的用量确定为 1 -15 % , VAC 的用量为 3 -15 %； 所述改性后的淀粉和聚合高分子进行接枝聚合步骤还进一步包括如下 步骤： 将经过改性的淀粉与改性后的聚合高分子及含有聚合高分子材料的 粘合剂， 在 20 "C-100 ， 最佳温度为 50° -65° C的容器中进行接枝聚 合在一起相互作用， 制出性能最优的天然植物淀粉胶合剂。
将上述制作好的粘合剂粘接木质产品的步骤如下：
在 -10 -50 °C的温度下， 将上述粘合剂涂在两件需粘结的木质产品表 面，在两件木质产品的另一侧表面施加 5公斤以上的压力，常温下可在 5-25 分钟达到表干， 24小时内固化， 该粘合剂能够粘贴住一切采用木质材料制 作的各种产品； 采用本发明的胶合剂粘贴的产品可浸水 48小时不开裂， 在 63 °C的水中煮 3小时不开裂， 标准试样剪切强度干强度可达到 5-14mpa， 湿强度达到 2- 7mpa。
上述的木质产品是下列产品之一： 木质家具、 布艺家具、 厨房家具、 胶合板、 密度板、 刨花板， 细木工板；
上述的装饰品是下列产品之一： 内墙涂料、 油漆及内墙腻子， 内墙磁 砖、 墙纸、 墙布、 地毯、 皮革。
上述粘结剂还可以应用在涂改液中。
本发明的有益效果： 采用本发明的方法， 能够粘贴住一切木质产品， 如木质家具、 布艺家具、 厨房家具、 胶合板、 细木工板、 密度板、 刨花板， 采用本发明的胶合剂粘贴的产品可浸水 48小时不开裂， 在 63 °C的水中煮 3 小时不开裂， 标准试样剪切强度干强度可达到 5-14mpa， 湿强度达到 2-7mpa, 还可作为内墙涂料、 油灰底子的粘胶剂， 可用于内墙磁砖、 墙纸、 墙布、 装饰贴纸、 地毯及皮革的粘合剂。
具体实施方式
本发明提供一种应用聚合粘合剂作为粘合剂粘接木质品或装饰品的方 法， 聚合胶合剂的成分 ^括淀粉和聚合高分子材料及其含有高分子聚合材 料的粘合剂， 制作粘合剂方法包括如下步骤： 将淀粉进行改性、 将聚合高 分子原料进行改性； 将改性后的淀粉及改性后的聚合高分子及含有高分子 聚合材料的粘合剂放置在温度为 20° C- 100° C，最佳温度为 45° -65° C的 容器中进行接枝聚合制成聚合胶合剂， 淀粉改性步骤可采用三级改性步骤 进行：
采用下列三级改性步骤中一个步骤或两个步骤或三个步骤进行改性， 可根据粘结剂的使用目的或场合来决定釆用其中的一个步骤或多个步骤来 进行改性， 在对粘结强度要求不高的， 可以只采用其中的一个步骤或两个 步骤来进行改性， 对于粘结强度要求高的产品， 可以采用三级步骤来进行 改性， 三级改性步骤的顺序可以改变， 下面介绍三级改性步骤的具体操作 流程： 三级改性的原理是依据淀粉分子中 Ci一 C6碳原子上可能起不同化学 反应的基团上进行， 经测定 C2、 C3、 C6上的羟基具有化学反应能力， 这是 淀粉大分子可被改性的内在因素， 已知一个淀粉分子含有 600-6000个葡萄 糖分子， 用单一的方法制出的改性淀粉胶只能是改性与未改性的混合淀粉 胶； 由此可以断定， 由单一改性后剩余的原淀粉， 可以加进其它助剂被继 续改性的可能性， 这是三级改性的理论基础及背景。
(-) . 淀粉的氧化改性：氧化的目的是将淀粉分子上的部分羟基（ 0H ) 氧化为醛基及羧基（C00H )， 可在 Ci一 C6碳原子上的基团上有选择性的 进行氧化， 氧化是在 PH值为 6-14的碱性淀粉水溶液中进行，氧化剂的用量 为 0. 8 - 10 % , 碱性淀粉水溶液的温度为 30° -100° C, 最佳温度为 40 ° - 55° C， 醛基具有防腐功能， 羧基对木质纤维具有增强粘接力的功能； (二) . 淀粉的糊化改性： 在碱性水溶液中进行， 糊化是在氧化的基础 上继续对淀粉分子中的剩余羟基进行改性； 改性方法是不断加入适量的碱 溶液， 使淀粉分子中的羟基 （0H ) 变成淀粉纳（st _0Na) , 这时反应系统 中的胶液则由稀变浓， 粘度也随之增高； 碱性溶液水的添加量确定为 1 一 15 %； 或 ΡΗ值达到 7-20， 碱性淀粉水溶液的温度为 30° C- 100° C, 最佳 温度为 50° -65。 Go
(三) . 淀粉的醚化改性： 是在淀粉分子中的某羟基与羟基化合物中的 一个羟基通过氧原子的联结形成另外一种淀粉衍生物； 添加醚化改性的改 性剂为酸类或环氧氯丙垸类； 在 30° C- 100° C, 最佳温度为 50° -65° C的 胶液中酸或环氧氯丙烷类与淀粉反应形成醚化淀粉衍生物， 酸或环氧氯丙 垸类的添加量为 1-15 % , 既增加粘性和韧性， 又具有一定的防腐功能， 增 加耐水性及胶接强度；
(四） 交联改性： 在胶液中加适量的尿素对淀粉分子可起交联作用， 在 40° -85° C, 最佳温度为 50° -65° C的胶液中， 尿素与淀粉分子中的醛 基或氧化过程中产生的醛基起縮合作用， 形成某种高聚物， 尿素的添加量 为 1 一 10 %， 对胶液的粘度与强度起一定辅助作用；
所述聚合高分子的改性进一步包括如下步骤： 将溶解的 PVA (聚乙稀 醇）或 PVAC (聚醋酸乙烯)乳化共聚改性， 乳化共聚法： 是将溶解的 PVA 或 PVAC溶液降温至 50 V -100 °C , 最佳温度为 65° -85° C, 加入乳化剂、 引发剂及适最的 VAC (乙酸乙稀）或 PA (聚丙烯酸纳）进行乳化聚合， 使 紧密相联的 PVA胶体形成分散型的乳胶粒， 降低粘度增加流动性。 引发剂 的用量确定为 1 -15 % ， VAC 的用量为 3 -15 %；
所述改性后的淀粉和聚合高分子进行接枝聚合步骤还进一步包括如下 步骤： 将经过改性的淀粉与改性的聚合高分子在 20 °C-100 °C， 最佳温度 为 45° -65 ° C 的容器中进行接枝聚合在一起相互作用，制作出性能最优的 天然植物淀粉胶合剂。
将上述制作好的粘结剂粘接木质产品的步骤如下- 在 -10 -50 。(：的温度下， 将上述粘合剂涂在两件需粘结的木质产品表 面，在两件木质产品的另一侧表面施加 5公斤以上的压力，常温下可在 5 - 25 分钟达到表干， 24小时内固化， 该粘合剂能够粘贴住一切采用木质材料制 作的各种产品； 采用本发明的胶合剂粘贴的产品可浸水 48小时不开裂， 在 63 的水中煮 3小时不开裂， 标准试样剪切强度干强度可达到 5- 14mpa， 湿强度达到 2- 7mpa。
该粘合剂可在 -10 -50 °C的温度下使用， 常温下可在 5-25分钟达到表 干， 24小时内固化， 标准试样施加 5公斤以上的压力， 能够粘贴住一切釆 用木质材料制作的各种产品， 如木质家具、 布艺家具、 厨房家具、 胶合板、 细木工板、 密度板、 刨花板， 采用本发明的胶合剂粘贴的产品可浸水 48小 时不开裂，在 63 °C的水中煮 3小时不开裂，标准试样剪切强度干强度可达 到 5-14mpa, 湿强度达到 2-7mpa， 还可作为内墙涂料、 油漆及内墙腻子的 粘胶剂， 可用于内墙磁砖、 墙纸、 装饰贴纸、 墙布、 地毯及皮革的粘合剂。

Claims

权 利 要 求
1、 一种应用聚合粘合剂作为粘合剂粘接木质品或装饰品的方法， 聚合 胶合剂中含有淀粉和聚合高分子材料或含有聚合高分子材料的粘合剂， 制 作粘合剂的方法如下： 将淀粉进行改性、 将聚合高分子进行改性； 将改性 后的淀粉和改性后的聚合高分子放置在温度为 20° -100° C, 最佳温度为 50° -65° C的容器中进行接枝聚合制成聚合胶合剂， 淀粉改性步骤包括如 下步骤：
淀粉的氧化改性： 氧化的目的是将淀粉分子上的部分羟基 （0H ) 氧化 为醛基及羧基（C00H )， 可在 d— Ce碳原子上的基团上有选择性的进行 氧化， 氧化是在 PH值为 6-14的碱性淀粉水溶液中进行氧化,氧化剂的用量 为 0. 8 - 10 %， 淀粉水溶液的温度为 30° -100° C, 最佳温度为 40° -55 0 C醛基具有防腐功能， 羧基对木质纤维具有增强粘接力的功能；
将上述制作好的粘结剂粘接木质产品的步骤如下- 在 -10 -50 °C的温度下， 将上述粘合剂涂在两件需粘结的木质产品表 面，在两件木质产品的另一侧表面施加 5公斤以上的压力，常温下可在 5-25 分钟达到表干， 24小时内固化， 该粘合剂能够粘贴住一切采用木质材料制 作的各种产品； 采用本发明的胶合剂粘贴的产品可浸水 48小时不开裂， 在 63 °C的水中煮 3小时不开裂， 标准试样剪切强度干强度可达到 5- 14mpa， 湿强度达到 2- 7mpa。
2、 根据权利要求 1所述的应用淀粉和聚合高分子材料作为粘合剂粘接 木质品的方法， 所述的木质产品是下列产品之一： 木质家具、 布艺家具、 厨房家具、 胶合板、 密度板、 细木工板、 刨花板。
3、 根据权利要求 1所述的应用淀粉和聚合高分子材料作为粘合剂粘接 装饰品的方法， 所述的装饰品是下列产品之一： 内墙涂料、 油漆及内墙腻 子， 内墙磁砖、 装饰贴纸、 墙纸、 墙布、 地毯、 皮革。
4、 根据权利要求 1所述的方法， 其特征在于， 所述淀粉改性步骤进一 步包括如下步骤：
将经过氧化改性后的淀粉溶液进行糊化改性： 糊化改性在碱性水溶液 中进行， 糊化是在氧化的基础上继续对淀粉分子中的剩余羟基进行改性； 改性方法是不断加入适量的碱溶液， 使淀粉分子中的羟基 （0H )变成淀粉 纳（st— 0Na)， 这时反应系统中的胶液则由稀变浓， 粘度也随之增高； 碱性 溶液水的添加量确定为 1 一 15 %，或 PH值在 7-20之间， 碱性淀粉水溶液 的温度为 30° C- 100° C, 最佳温度为 50° -65° C。
5、 根据权利要求 4所述的方法， 其特征在于， 所述淀粉改性步骤还进 一步包括如下步骤：
将糊化改性后的淀粉再进行醚化改性： 是将淀粉分子中的某羟基与羟 基化合物中的一个羟基通过氧原子的联结形成另外一种淀粉衍生物； 添加 醚化改性的改性剂为酸类或环氧氯丙烷类； 在 30° -90° C, 最佳温度为 50 ° -65° C的胶液中酸或环氧氯丙垸类与淀粉反应形成醚化淀粉衍生物， 酸 或环氧氯丙烷类的添加量为 1-15 % , 既增加粘性和韧性， 又具有一定的防 腐功能， 增加耐水性及胶接强度；
将经过醚化改性的淀粉进行交联改性： 在胶液中加适量的尿素对淀粉 分子可起交联作用， 在 40° -85° C, 最佳温度为 50° -65° C的胶液中， 尿 素与淀粉分子中的醛基或氧化过程中产生的醛基起缩合作用， 形成某种高 聚物， 尿素的添加量为 1 一 10 % , 对胶液的粘度与强度起一定辅助作用。
6. 根据权利要求 1所述的方法， 其特征在于： 所述的聚合高分子的改 性进一步包括如下步骤： 将溶解的 PVA (聚乙稀醇） 或 PVAC (聚醋酸乙烯) 或其它聚合高分子材料进行乳化共聚改性，乳化共聚法：是将溶解的 PVA或 PVAC溶液降温至 50 °C -90 。C ， 最佳温度为 65 ° -80° C,' 加入乳化剂、 引发剂及适最的 VAC (乙酸乙稀）或 PA (聚丙烯酸纳）进行乳化聚合， 使 紧密相联的 PVA胶体形成分散型的乳胶粒， 降低粘度增加流动性。 引发剂 的用量确定为 1 -15 % , VAC 的用量为 3 -15 %。
7. 根据权利要求 1的方法， 其特征在于： 所述改性后的淀粉和聚合高 分子进行接枝聚合步骤还进一步包括如下步骤:
将经过改性的淀粉与改性的聚合高分子或含有聚合高分子材料的粘合剂在 20 °C-100 °C，最佳温度为 60° -80° C 的容器中进行接枝聚合在一起相互 作用， 制作出性能最优的天然植物淀粉胶合剂。
PCT/CN2005/001957 2005-03-31 2005-11-18 Procede pour l’application d’adhesif polymere en tant qu’agent adhesif pour coller du bois ou une garniture WO2006102809A1 (fr)

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