WO1992019661A1 - Resine d'uree cocondensee - Google Patents

Resine d'uree cocondensee Download PDF

Info

Publication number
WO1992019661A1
WO1992019661A1 PCT/JP1991/000590 JP9100590W WO9219661A1 WO 1992019661 A1 WO1992019661 A1 WO 1992019661A1 JP 9100590 W JP9100590 W JP 9100590W WO 9219661 A1 WO9219661 A1 WO 9219661A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
urea
mol
weight
condensation
Prior art date
Application number
PCT/JP1991/000590
Other languages
English (en)
Japanese (ja)
Inventor
Yoshiyasu Yamagishi
Hiroaki Yoshida
Kinji Taki
Seinosuke Horiki
Original Assignee
Nagoya Oilchemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nagoya Oilchemical Co., Ltd. filed Critical Nagoya Oilchemical Co., Ltd.
Priority to PCT/JP1991/000590 priority Critical patent/WO1992019661A1/fr
Priority to DE4193551T priority patent/DE4193551T1/de
Priority to CA002086418A priority patent/CA2086418A1/fr
Publication of WO1992019661A1 publication Critical patent/WO1992019661A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/08—Ureas; Thioureas

Definitions

  • the present invention relates to a urea-based co-condensation resin which is inexpensive and has remarkably improved water resistance, weather resistance, boiling resistance and workability, and the urea-based co-condensation resin is made of wood, fiber, paper, glass fiber, etc. It is useful as an adhesive or binder for organic or inorganic materials.
  • urea resins used for bonding wood and the like are inferior in water resistance.
  • co-condensation resins obtained by co-condensing urea with melamine, phenol and the like have been provided.
  • the water resistance of these co-condensation resins was improved, the boiling resistance and weather resistance were still insufficient.
  • various attempts have been made to co-condensate urea with a polyvalent phenol such as resorcin.However, since the reaction rates of urea and polyvalent phenol monomers differ greatly from aldehyde, it is extremely difficult to co-condense. It has been considered difficult and it is virtually impossible to obtain a co-condensation resin of urea and polyhydric phenol.
  • urea resin and polyhydric phenol monomer for example, Japanese Patent Publication No. 57-960
  • urea resin and polyhydric phenol A resin mixture with an phenolic resin for example, Japanese Patent Publication No. 58-234425
  • water resistance and boiling resistance are improved
  • other modifying resins, organic / inorganic fillers, thickeners, curing agents or curing catalysts, etc. were added at the time of use.
  • the compatibility may be poor, the viscosity may increase, or mixing may not be possible.In some cases, the pot life after blending may be shortened, resulting in inconvenience such as poor workability. there were.
  • the polyhydric phenol of the present invention refers to one or more polyhydric phenols such as resorcinol, alkyl resorcinol, pyrogallol, catechol, alkyl catechol, dyloquinone, alkylhydroquinone, floroglucin, bisphenol, dihydroxynaphthalin and the like.
  • alkyl resorcinol examples include 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5—n-butyl resorcinol, 4,5-dimethyl resorcinol, 2,5-dimethyl resorcinol, 4,5—j Tilresorcinol, 2,5-getylresorcinol, 4,5-dipropylresorcinol, 2,5-dipi ⁇ pyrresorcinol, 4-methyl-1-5-ethyl resorcinol, 2-methyl-1 5-ethylethylresorcinol, 2 —Methyl-5-propyl resorcinol, 2, 4, 5—trimethyl resorcinol, 2,4,5-triethyl resorcinol, etc., but above all, 5-methyl resorcinol is particularly easy to co-condensate with urea and low A co-condensation resin
  • Aldehyde donors include formalin, formaldehyde, paraformaldehyde, trioxane, acetoaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butylaldehyde, Turnip aldehyde, benzaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, 0-tolualdehyde, sultylaldehyde, etc., compounds having an aldehyde group or compounds that decompose to release aldehyde groups upon heating One or a mixture of two or more is exemplified.
  • a polyhydric phenol particularly an alkylresorcin such as 5-methylresorcin
  • a complexing agent for relaxing the reaction may be added.
  • complexing agents include phenol of polyvalent phenol.
  • a compound having a ketone group or an amide group capable of forming a complex with a thiol group and examples thereof include acetone and thioprolactam.
  • acetone is a preferred complexing agent.
  • the amount of the complexing agent to be added is not particularly limited, but usually about 0.4 to 0.8 mol per 1 mol of the polyvalent phenol is desirable.
  • the co-condensation resin of the present invention 0.2 to 2.0 moles, preferably 0.4 to 2.0 moles of the polyhydric phenol per mole of urea and, if necessary, 0.1 to 0.1 moles of the complexing agent. 6 to 1.6 And the pH is adjusted to 4.0 to 9.0, preferably 8.0 to 8.5 with an acid or alkali, and then 0.1 to 2.0 mol of an aldehyde donor is added to the mixture. The reaction is usually heated at 75 to 80 ° C. After the reaction is completed, it is desirable to cool the reaction mixture to room temperature and adjust the pH to about 8.0.
  • the polyhydric phenol is less than 0.2 mol, a large amount of unreacted urea remains in the obtained resin, and a resin having water resistance and boiling resistance cannot be obtained, or 2.0 mol or more. If it is, the stability of the obtained resin is deteriorated. Further, when the polyvalent phenol is less than 0.4 mol, unreacted urea remains in the co-condensate depending on the type of the polyvalent phenol, and the performance of the resin may be deteriorated. It is desirable that the amount of the metal added be 0.4 to 2.0 mol.
  • the third component when the third component is added to the co-condensation resin of the present invention, the third component may be added to the reaction system before the condensation reaction. It may be added later.
  • an aldehyde donor 1 5 to 80 parts by weight are added and mixed.
  • synthetic rubber such as SBR, NBR, CR
  • various synthetic resins such as vinyl acetate resin, acrylic resin, urethane resin, CMC, PVA
  • Fillers such as starch, nika, gelatin, blood powder, walnut powder, coconut powder, flour, calcium carbonate, talc, gypsum, pigments, dyes, flame retardants, insect repellents, preservatives, and other third substances Add and mix.
  • composition containing the co-condensation resin of the present invention obtained by the above composition is applied as an adhesive, a binder, and a coating agent, and is cured at room temperature or under heat. In particular, when heated to 100 ° C. or more, it cures in an extremely short time, and forms a cured resin product having excellent adhesion to woody and fibrous materials.
  • the co-condensation resin of the present invention is made of wood such as plywood, laminated wood, particle board, corrugated cardboard, felt, non-woven fabric, fiber, paper, glass fiber, rock wool, organic matter such as ceramic fiber or carbon fiber, It can be used as an inorganic material adhesive, binder, coating agent, etc.
  • the curing of the co-condensation resin of the present invention does not require the addition of an acidic curing catalyst, so that the resin is kept neutral, and the resin cured product is converted into residual acid even after a long period of use.
  • an acidic curing catalyst so that the resin is kept neutral, and the resin cured product is converted into residual acid even after a long period of use.
  • the co-condensation resin according to the present invention is different from the conventional urea resin due to co-condensation with a polyhydric phenol, and has water resistance and boiling resistance close to the performance of the polyhydric phenol resin such as resorcinol and alkylresorcinol, Weather resistance is obtained.
  • the curing speed was too high and the pot life was short, so that hexamethylenetetramine had to be used as a curing agent.
  • the pot life when adding paraformaldehyde is 2 hours or more, and the resin cures at room temperature. Further, when heated, curing is completed in a relatively short time at a relatively low temperature of 100 to 120 ° C. Therefore, the workability of the co-condensation resin of the present invention is extremely good.
  • the density of cross-links formed between urea and aldehyde by co-condensation with polyvalent phenol decreases, the resin itself becomes soft, and the stress accompanying the curing shrinkage of the resin is reduced. And the resulting cured resin layer is less likely to crack, deform, etc., and has excellent durability.
  • Example 2 In place of 5-methylresorcin used in Example 1, 55 parts by weight (0.5 mol) of resorcinol was used, and other conditions were obtained by co-condensing under the same mixing ratio and reaction conditions as in Example 1. Using the obtained resin (sample 2), a plywood similar to that of Example 1 was prepared, and the results of an adhesive strength test are shown in Table 2.
  • Example 3 For comparison with Example 3, the normal 50% urea resin 1 The same test as in Example 3 was conducted for an adhesive prepared by adding 0.6 parts by weight of ammonium chloride as a curing agent to 100 parts by weight, and the results are shown in Table 3.
  • Flexibility Flexible and unchanging when bent at 20 ° from the center of a test piece of width 50 hidden and length 300 mm, ⁇ , broken and broken one that does not break, What was soiled was X.
  • Example 4 For comparison with Example 4, a mixture of 80% by weight of a usual 50% urea resin and 20% by weight of a 50% alkylresorcin resin was mixed with 15 parts by weight of walnut powder and 3 parts by weight of paraform as a curing agent. The same test as in Example 4 was performed for the adhesive with the addition and adjustment of the parts, and Table 4 shows the results.
  • the co-condensation resin according to the present invention has good adhesion, water resistance and boiling resistance, and among the polyhydric phenols, resorcinol It can be seen that the resin using alkylresorcin has more flexibility.
  • Example 4 also shows that the pot life is longer and the workability is better than when the urea resin and the polyvalent phenol resin are blended.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Résine d'urée cocondensée produite par cocondensation d'urée avec un phénol polyhydrique, cela conférant à ladite résine d'urée une meilleure résistance à l'eau, aux intempéries, à l'ébullition, et également une meilleure aptitude au façonnage. Bien qu'il soit difficile de cocondenser de l'urée avec un phénol polyhydrique, il est possible, grâce à l'invention, d'obtenir facilement une résine cocondensée par réaction d'un mol d'urée avec 0,2 à 2,0 mol d'un phénol polyhydrique et 0,1 à 2,0 mol d'un donneur aldéhyde, ladite réaction se faisant sous chauffage et dans une plage de pH comprise entre 4 et 9.
PCT/JP1991/000590 1991-04-30 1991-04-30 Resine d'uree cocondensee WO1992019661A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/JP1991/000590 WO1992019661A1 (fr) 1991-04-30 1991-04-30 Resine d'uree cocondensee
DE4193551T DE4193551T1 (fr) 1991-04-30 1991-04-30
CA002086418A CA2086418A1 (fr) 1991-04-30 1991-04-30 Resine d'uree cocondensee

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1991/000590 WO1992019661A1 (fr) 1991-04-30 1991-04-30 Resine d'uree cocondensee

Publications (1)

Publication Number Publication Date
WO1992019661A1 true WO1992019661A1 (fr) 1992-11-12

Family

ID=4150917

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1991/000590 WO1992019661A1 (fr) 1991-04-30 1991-04-30 Resine d'uree cocondensee

Country Status (3)

Country Link
CA (1) CA2086418A1 (fr)
DE (1) DE4193551T1 (fr)
WO (1) WO1992019661A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4854148A (fr) * 1971-11-03 1973-07-30
JPS579600B2 (fr) * 1977-03-23 1982-02-22
JPS5845216A (ja) * 1981-06-19 1983-03-16 バスフ・アクチエンゲゼルシヤフト 塩基性窒素基を有する重付加／重縮合生成物
JPS5845217A (ja) * 1981-06-19 1983-03-16 バスフ・アクチエンゲゼルシヤフト 塩基性窒素基を有する重付加／重縮合生成物
JPS5823425B2 (ja) * 1975-10-21 1983-05-14 ナゴヤユカガクコウギヨウ カブシキガイシヤ セツチヤクザイソセイブツ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4854148A (fr) * 1971-11-03 1973-07-30
JPS5823425B2 (ja) * 1975-10-21 1983-05-14 ナゴヤユカガクコウギヨウ カブシキガイシヤ セツチヤクザイソセイブツ
JPS579600B2 (fr) * 1977-03-23 1982-02-22
JPS5845216A (ja) * 1981-06-19 1983-03-16 バスフ・アクチエンゲゼルシヤフト 塩基性窒素基を有する重付加／重縮合生成物
JPS5845217A (ja) * 1981-06-19 1983-03-16 バスフ・アクチエンゲゼルシヤフト 塩基性窒素基を有する重付加／重縮合生成物

Also Published As

Publication number Publication date
CA2086418A1 (fr) 1992-10-31
DE4193551T1 (fr) 1993-05-13

Similar Documents

Publication Publication Date Title
US4003873A (en) Cement-phenolic resin compositions
JPH01158022A (ja) リグニン−フェノール樹脂組成物
JP5775306B2 (ja) 改質フェノール樹脂
US5637658A (en) Modified phenol-aldehyde resin and binder system
US5910521A (en) Benzoxazine polymer composition
AU2002339806B2 (en) Method of gluing wood based materials
US3896081A (en) Rapid curing resin compositions employing aminoplast condensation polymer modified with a di-substituted bis-aryl amine
JPS5817515B2 (ja) 接着剤組成物
CN107429038A (zh) 甲阶改性酚醛树脂组合物、其制造方法和粘合剂
EP1122268B1 (fr) Composition de polymère pour faire durcir des résines novolaques
US6667104B2 (en) Phenol resin composition for wet friction material and wet friction material
WO1992019661A1 (fr) Resine d'uree cocondensee
JPH01158021A (ja) リグノセルロース−フェノール樹脂組成物
JP3856344B2 (ja) 尿素・アルデヒド系樹脂の硬化方法
JP3256034B2 (ja) アミノ系共縮合樹脂接着剤およびその製造方法
JP2001164228A (ja) 木材用接着剤組成物
JP2001254065A (ja) 木材用接着剤組成物
JPH10512618A (ja) 可とう化したフェノール樹脂、その製造方法および使用
JPH07118355A (ja) 硬化性混合組成物および該組成物を用いた構造材
JP3654689B2 (ja) 熱硬化性樹脂組成物、硬化方法、木質材料および成形物
JP3729469B2 (ja) 硬化性樹脂組成物の製造方法
JPS6158484B2 (fr)
JPS6221019B2 (fr)
JPH11131038A (ja) 木材用接着剤の製造方法
JP2001254066A (ja) フェノール樹脂接着剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA DE FI JP SE US

WWE Wipo information: entry into national phase

Ref document number: 2086418

Country of ref document: CA

RET De translation (de og part 6b)

Ref document number: 4193551

Country of ref document: DE

Date of ref document: 19930513

WWE Wipo information: entry into national phase

Ref document number: 4193551

Country of ref document: DE