JPH0238622B2 - TAISUISEIFUYOZAINOSEIZOHOHO - Google Patents
TAISUISEIFUYOZAINOSEIZOHOHOInfo
- Publication number
- JPH0238622B2 JPH0238622B2 JP70282A JP70282A JPH0238622B2 JP H0238622 B2 JPH0238622 B2 JP H0238622B2 JP 70282 A JP70282 A JP 70282A JP 70282 A JP70282 A JP 70282A JP H0238622 B2 JPH0238622 B2 JP H0238622B2
- Authority
- JP
- Japan
- Prior art keywords
- wax
- formula
- emulsifier
- resin
- pressure
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 13
- 239000012188 paraffin wax Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004200 microcrystalline wax Substances 0.000 claims description 4
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000004203 carnauba wax Substances 0.000 claims description 3
- 235000013869 carnauba wax Nutrition 0.000 claims description 3
- 239000012170 montan wax Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 7
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229940114937 microcrystalline wax Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003443 succinic acid derivatives Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は硬化促進剤として硫酸アンモニウムを
含むホルムアルデヒド縮合系接着剤の耐水性付与
剤の製造方法に関する。
現在ホルムアルデヒド縮合系接着剤は有機質板
の接着剤として用いられており、耐水性付与剤と
してパラフインワツクスエマルジヨンが使用され
ていた。しかしこのような接着剤用の硬化促進剤
として塩化アンモニウムは溶解度が低いため、硬
化促進剤として塩化アンモニウムを用いる時、得
られる接着剤は低濃度すなわち固形分含有量が少
ない。しかし固形分濃度が少ない接着剤では乾燥
に長時間を要する等の欠点がある。有機質板の接
着剤としては固形分濃度が高いことが望ましい。
硬化促進剤として塩化アンモニウムの代りの溶
解度の大きい硫酸アンモニウムを使用することが
考えられる。しかし硬化促進剤として硫酸アンモ
ニウムを使用し、かつ耐水性付与剤としてパラフ
インワツクスエマルジヨンを使用したホルムアル
デヒド縮合系接着剤においては接着剤/塩化アン
モニウム硬化促進剤/耐水性付与剤の相溶性が悪
く乳化状態が破壊しやすい。
本発明者は、硬化促進剤として硫酸アンモニウ
ムを使用するホルムアルデヒド縮合系接着剤用の
耐水性付与剤について研究を行なつた結果、特定
な製造方法によつて製造された水性エマルジヨン
を耐水性付与剤として使用すると硫酸アンモニウ
ムを含むホルムアルデヒド縮合系接着剤の乳化状
態が破壊されないことを発見し、本発明に至つ
た。本発明はナフサ分解時に副生される−20℃〜
250℃の留分をフリーデルクラフト型反応により
重合して得た軟化点常温〜150℃の樹脂、その樹
脂のα・β不飽和多塩基性酸付加物、又はパラフ
インワツクス、酸化パラフイン、マイクロクリス
タリンワツクス、カルナバロウ、モンタンロウ、
ポリエチレンワツクなる群から選ばれた少なくと
も1種のワツクスに乳化剤を1〜15wt%使用し
加圧下で乳化を行なうことを特徴とした硬化促進
剤として硫酸アンモニウムを含むホルムアルデヒ
ド縮合系接着剤用の耐水性付与剤の製造方法に関
する。
本発明において原料としてナフサ分解時に副生
される沸点−20〜250℃の留分をフリーデルクラ
フト型反応により重合して得られた軟化点常温〜
150℃好ましくは40℃〜100℃の樹脂或はその樹脂
のα・β不飽和多塩基性酸付加物が使用される。
α・β不飽和多塩基性酸としてはマレイン酸、無
水マレイン酸、フマル酸、イタコン酸などが掲げ
られる)或は、パラフインワツクス、酸化パラフ
イン、マイクロクリスタリンワツクス、カルナバ
ロウ、モンタンロウ、ポリエチレンワツクス等又
はこれらの混合物が用いられる。
次に乳化剤としてはフエノール、アルキルフエ
ノールのベンジル化物、或はスチリル化物、又は
これらのホルムアルデヒド、アセトアルデヒド縮
合物、或はナフトール、フエニルフエノールのベ
ンジル化物、或はスチリル化物にエチレンオキサ
イド或はプロピレンオキサイド或はエチレンオキ
サイド/プロピレンオキサイドを上記疎水性物質
の−OH基1モル当量に対し2〜40モルの範囲で
付加重合させたもの或はそのスルホン酸塩(K,
Na,NH4,N(CH2CH2OH)3,
The present invention relates to a method for producing a water resistance imparting agent for a formaldehyde condensation adhesive containing ammonium sulfate as a curing accelerator. At present, formaldehyde condensation adhesives are used as adhesives for organic boards, and paraffin wax emulsion has been used as a water resistance imparting agent. However, since ammonium chloride has low solubility as a curing accelerator for such adhesives, when ammonium chloride is used as a curing accelerator, the resulting adhesive has a low concentration, that is, a low solid content. However, adhesives with a low solid content concentration have drawbacks such as requiring a long time to dry. It is desirable that the adhesive for organic boards has a high solid content concentration. It is conceivable to use highly soluble ammonium sulfate instead of ammonium chloride as a hardening accelerator. However, in formaldehyde condensation adhesives that use ammonium sulfate as a curing accelerator and paraffin wax emulsion as a water resistance imparting agent, the adhesive/ammonium chloride curing accelerator/water resistance imparting agent have poor compatibility and emulsion. The condition is easily destroyed. As a result of research on water resistance imparting agents for formaldehyde condensation adhesives that use ammonium sulfate as a curing accelerator, the present inventors discovered that water-based emulsions produced by a specific manufacturing method were used as water resistance imparting agents. It was discovered that the emulsified state of a formaldehyde condensation adhesive containing ammonium sulfate is not destroyed when used, leading to the present invention. This invention is a by-produced product during naphtha decomposition, from -20°C to
Resin with a softening point of room temperature to 150°C obtained by polymerizing a 250°C fraction by Friedel-Crafts type reaction, an α/β unsaturated polybasic acid adduct of the resin, paraffin wax, oxidized paraffin, micro Crystalline wax, carnauba wax, montan wax,
Water resistance imparted to formaldehyde condensation adhesives containing ammonium sulfate as a curing accelerator, characterized by using 1 to 15 wt% of an emulsifier in at least one wax selected from the group of polyethylene waxes and emulsifying under pressure. The present invention relates to a method for producing a drug. In the present invention, the softening point of the raw material obtained by polymerizing the fraction with a boiling point of -20 to 250°C, which is produced as a by-product during naphtha decomposition, by a Friedel-Crafts type reaction is from room temperature to
A resin having a temperature of 150°C, preferably 40°C to 100°C, or an α/β unsaturated polybasic acid adduct of the resin is used.
(α/β unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc.) or paraffin wax, oxidized paraffin, microcrystalline wax, carnauba wax, montan wax, polyethylene wax etc. or a mixture thereof may be used. Next, as an emulsifier, phenol, a benzylated product of alkylphenol, or a styryl product, or a formaldehyde or acetaldehyde condensate thereof, or a benzylated product or styryl product of naphthol or phenylphenol, and ethylene oxide, propylene oxide, or is an addition polymerized product of ethylene oxide/propylene oxide in a range of 2 to 40 moles per mole equivalent of -OH group of the above hydrophobic substance, or its sulfonate (K,
Na, NH 4 , N(CH 2 CH 2 OH) 3 ,
【式】など)又はコハク酸誘導体
の塩を1.0〜15wt%好ましくは2.0〜10wt%用いら
れる。
乳化剤の具体例は次の通りである。
下記の一般式[Formula] etc.) or a salt of a succinic acid derivative is used in an amount of 1.0 to 15 wt%, preferably 2.0 to 10 wt%. Specific examples of emulsifiers are as follows. The general formula below
【式】
(但し式中Rはベンゼン環を2〜3個有するア
リール基、アルキルアリール基、R′はエチレン
基または/及びプロピレン基、nは5〜40の整数
およびMは水素原子、一価の金属原子又はアンモ
ニウム基を表わす。)
で示される化合物を乳化剤として用いることを提
供するものである。
一般式で示される化合物は、ベンゼン環を2〜
3個有するアリールフエノール又はアルキルアリ
ールフエノールに酸化エチレン又は/及び酸化プ
ロピレンを付加重合せしめて、しかる後に無水マ
レイン酸でエステル化し、さらに酸性亜硫酸塩又
は亜硫酸塩でスルホン化することによつて得られ
る。一般式で示される化合物製造の出発原料とな
るフエノール類を例示すると下記のものを挙げる
ことができる。
a オルソ、メタ、パラ−フエニルフエノール、
α・β―ナフトール
b フエノール、アルキルフエノールのベンジル
化物
例[Formula] (In the formula, R is an aryl group or alkylaryl group having 2 to 3 benzene rings, R' is an ethylene group or/and a propylene group, n is an integer from 5 to 40, and M is a hydrogen atom, monovalent represents a metal atom or an ammonium group) as an emulsifier. The compound represented by the general formula has 2 to 2 benzene rings.
It is obtained by addition-polymerizing ethylene oxide or/and propylene oxide to an arylphenol or alkylarylphenol having three phenols, followed by esterification with maleic anhydride, and further sulfonation with an acidic sulfite or sulfite. Examples of phenols that can be used as starting materials for producing the compound represented by the general formula include the following. a Ortho, meta, para-phenylphenol,
α・β-Naphthol b Examples of benzylated phenols and alkylphenols
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
c フエノール、アルキルフエノールのスチリル
化物
(例)[Formula] c Styryl compound of phenol or alkylphenol (example)
【式】【formula】
【式】【formula】
【式】
d ナフトール、フエニルフエノールのベンジル
化物
(例)[Formula] d Naphthol, benzylated product of phenylphenol (example)
【式】【formula】
【式】
e ナフトール、フエニルフエノールのスチリル
化物
(例)[Formula] e Naphthol, styryl compound of phenylphenol (example)
【式】【formula】
【式】 かかるアリールフ
エノール、アルキルアリールフエノールに付加重
合される酸化エチレン又は/及び酸化プロピレン
はフエノール類1モルに対し5〜40モルの範囲付
加重合させたものが用いられる。酸化プロピレン
のみの場合は性能的に若干問題があり酸化プロピ
レン量としては酸化エチレン+酸化プロピレン量
の50%以下であることが必要である。特に好まし
い範囲はアリールフエノール、アルキルアリール
フエノールの重量に対し酸化エチレンを2〜4倍
量、酸化プロピレンを0〜2倍量に相当するモル
数が好ましい。かくして得られたポリオキシエチ
レン(ポリオキシプロピレン)、アリールフエノ
ールエーテル、ポリオキシエチレン(ポリオキシ
プロピレン)アルキルアリールフエノールエーテ
ルに対して無水マレイン酸を反応させ得られたエ
ステル化物に対し酸性亜硫酸塩又は亜硫酸塩を反
応せしめることによつて本発明の化合物が得られ
るが酸性亜硫酸塩、又は亜硫酸塩はリチウム塩、
ナトリウム塩、カリウム塩、又はアンモニウム塩
が使用されるが経済的にはナトリウム塩が好まし
い。本発明の水性エマルジヨンに使用されるロジ
ン及びロジン誘導体としては、カムロジン、トー
ル油ロジン、ウツドロジン、重合ロジン、水添ロ
ジン等のホルムアルデヒド多塩基乳化剤が従来公
知の乳化剤の欠点を克服し最も優れた効果を発揮
する事を見い出した。
本発明はロジン及びロジン誘導体より水性エマ
ルジヨンを製造する為、又必要に応じて水酸化カ
リウム、水酸化ナトリウム、アルカノールアミ
ン、モルホリンなどを用いる事も出来る。乳化方
法に関しては、前述の樹脂或はワツクス或はそれ
らの混合物を60℃〜150℃好ましくは70℃〜120℃
に溶解後乳化剤を1.0〜15wt%好ましくは2.0〜
10wt%加え混融した後常圧或は加圧下で温水を
加えて予備乳化を行なつた後高圧乳化機を用いて
100Kg/cm2の圧力下、好ましくは150Kg/cm2〜300
Kg/cm2の圧力下で1回又は2回通した後冷却し固
型分40〜60%の水性エマルジヨンを得る。
本発明におけるホルムアルデヒド縮合系接着剤
とは尿素樹脂接着剤、メラミン系接着剤等の公知
のホルムアルデヒド縮合系接着剤を意味する。
以下詳細は、実施例を持つて説明するが、その
範囲に限定するものではない。
実施例 (1)
ナフサ分解時に副生される沸点−20℃〜250℃
の留分をフリーデルクラフト型反応により得られ
た軟化点63℃の樹脂96部を撹拌機付反応釜に仕込
み加熱溶融した後無水マレイン酸を1.0部加え200
℃±5℃で4時間反応を行なつた。反応終了後上
記反応物を撹拌機付乳化釜に移送して系内の温度
を90℃に冷却し、続いて乳化剤として30%に溶解
したポリオキシエチレンスチリル化フエノールエ
ーテルスルホン酸ナトリウムを10部と49%水酸化
カリウム20部を加えケン化した後80℃の温水を73
部加え乳化を行なつた。然る後ピストン型高圧乳
化機を用いて250Kg/cm2の圧力で2回通し急冷を
行なつて固型分50%の白色エマルジヨンを得た。
実施例 (2)
撹拌機付乳化釜に融点25℃のパラフインワツク
スを95部仕込み加熱溶融した後乳化剤として25%
solidポリオキシエチレン/プロピレンベンジル
化フエニルフエノールエーテルスルホン酸アンモ
ニウム20部加え混合した後70℃の温水を51部加え
乳化を行なう。乳化終了後ピストン型高圧乳化機
を用いて300Kg/cm2の圧力で2回通した後急冷し
固型分60%の白色エマルジヨンを得た。
実施例 (3)
撹拌機付乳化釜に融点62℃のパラフインワツク
ス80部と融点83℃のマイクロクリスタリンワツク
ス10部を仕込み加熱溶融した後30%水溶液とした
ポリオキシエチレンスチリル化フエノールエーテ
ルスルホン酸アンモニウム33部を加え混合した後
90℃の温水を58部を加え乳化を行なう。然る後ピ
ストン型高圧乳化機を用いて300Kg/cm3の圧力で
1回通し、急冷を行ない固型分55%の白色エマル
ジヨンを得た。
上記の実施例で得られた耐水性付与剤について
以下のようなテストを行なつた。
4−1 試験方法
4−1−1 接着剤:尿素樹脂(固型分66%)
4−1−2 耐水化剤添加量:対接着剤(有
姿)2.5wt%solid
4−1−3 硬化促進剤添加量:対接着剤
6wt%(塩化アンモニウム)
4−1−4 板厚:150mm
4−2 試験項目
4−2−1 比重
4−2−2 含水率(%)
4−2−3 曲げ強さ〔Kg/cm2〕
4−2−4 剥離低抗〔Kg/cm2〕
4−2−5 木ネジ保持力〔Kg〕
4−2−6 ホルムアルデヒド放出量
〔mg/Kg〕[Formula] Ethylene oxide or/and propylene oxide to be addition-polymerized to the arylphenol or alkylarylphenol is added in an amount of 5 to 40 moles per mole of the phenol. When only propylene oxide is used, there are some performance problems, and the amount of propylene oxide needs to be 50% or less of the amount of ethylene oxide + propylene oxide. A particularly preferable range is a mole number corresponding to 2 to 4 times the amount of ethylene oxide and 0 to 2 times the amount of propylene oxide relative to the weight of the arylphenol or alkylarylphenol. The polyoxyethylene (polyoxypropylene), aryl phenol ether, and polyoxyethylene (polyoxypropylene) alkylaryl phenol ether thus obtained are reacted with maleic anhydride, and the resulting esterified product is treated with acidic sulfite or sulfite. The compounds of the present invention can be obtained by reacting salts, but acidic sulfites, or sulfites are lithium salts,
Sodium salts, potassium salts, or ammonium salts may be used, with the sodium salt being economically preferred. As the rosin and rosin derivatives used in the aqueous emulsion of the present invention, formaldehyde polybasic emulsifiers such as camrosin, tall oil rosin, uddrosin, polymerized rosin, and hydrogenated rosin overcome the drawbacks of conventionally known emulsifiers and have the most excellent effect. I discovered that it can demonstrate the In the present invention, since an aqueous emulsion is produced from rosin and rosin derivatives, potassium hydroxide, sodium hydroxide, alkanolamine, morpholine, etc. can also be used as necessary. Regarding the emulsification method, the above-mentioned resin or wax or mixture thereof is heated at 60°C to 150°C, preferably 70°C to 120°C.
After dissolving the emulsifier in 1.0~15wt% preferably 2.0~
After adding 10wt% and mixing, pre-emulsify by adding warm water under normal pressure or pressurization, and then use a high-pressure emulsifier.
Under pressure of 100Kg/ cm2 , preferably 150Kg/ cm2 to 300
It is passed once or twice under a pressure of Kg/cm 2 and then cooled to obtain an aqueous emulsion with a solids content of 40-60%. The formaldehyde condensation adhesive in the present invention refers to known formaldehyde condensation adhesives such as urea resin adhesives and melamine adhesives. The details will be explained below with reference to examples, but the scope is not limited thereto. Example (1) Boiling point of by-products during naphtha decomposition -20°C to 250°C
96 parts of a resin with a softening point of 63°C obtained by Friedel-Crafts type reaction were charged into a reaction vessel equipped with a stirrer, heated and melted, and then 1.0 part of maleic anhydride was added to 200°C.
The reaction was carried out at ±5°C for 4 hours. After the completion of the reaction, the above reactant was transferred to an emulsification tank equipped with a stirrer and the temperature inside the system was cooled to 90°C, and then 10 parts of sodium polyoxyethylene styrylated phenol ether sulfonate dissolved at 30% as an emulsifier was added. After adding 20 parts of 49% potassium hydroxide and saponifying it, add 80℃ hot water to 73℃.
emulsification was carried out. Thereafter, the mixture was rapidly cooled by passing it twice at a pressure of 250 kg/cm 2 using a piston-type high-pressure emulsifier to obtain a white emulsion with a solid content of 50%. Example (2) 95 parts of paraffin wax with a melting point of 25°C was charged into an emulsifying pot with a stirrer, heated and melted, and then 25% was added as an emulsifier.
After adding 20 parts of solid polyoxyethylene/propylene benzylated phenylphenol ether ammonium sulfonate and mixing, 51 parts of 70°C warm water was added to emulsify. After emulsification, the mixture was passed through a piston-type high-pressure emulsifier twice at a pressure of 300 kg/cm 2 and then rapidly cooled to obtain a white emulsion with a solid content of 60%. Example (3) 80 parts of paraffin wax with a melting point of 62°C and 10 parts of microcrystalline wax with a melting point of 83°C were placed in an emulsifying pot with a stirrer, heated and melted, and then made into a 30% aqueous solution of polyoxyethylene styrylated phenol ether sulfone. After adding 33 parts of ammonium acid and mixing
Add 58 parts of 90°C warm water to emulsify. Thereafter, the mixture was passed once under a pressure of 300 kg/cm 3 using a piston type high-pressure emulsifying machine and rapidly cooled to obtain a white emulsion with a solid content of 55%. The following tests were conducted on the water resistance imparting agent obtained in the above examples. 4-1 Test method 4-1-1 Adhesive: Urea resin (solid content 66%) 4-1-2 Addition amount of water resistant agent: 2.5 wt% solid to adhesive (visible) 4-1-3 Curing Accelerator addition amount: for adhesive
6wt% (ammonium chloride) 4-1-4 Plate thickness: 150mm 4-2 Test items 4-2-1 Specific gravity 4-2-2 Moisture content (%) 4-2-3 Bending strength [Kg/cm 2 ] 4-2-4 Low peeling resistance [Kg/cm 2 ] 4-2-5 Wood screw holding force [Kg] 4-2-6 Formaldehyde release amount
[mg/Kg]
【表】
4−4 結果
硬化促進剤として硫酸アンモニウムを対接着剤
8wt%で使用した以外は上記と同一の条件で試験
を行なつた。[Table] 4-4 Results Using ammonium sulfate as a curing accelerator for adhesives
The test was conducted under the same conditions as above except that 8 wt% was used.
【表】
対照テストとして市販のパラフインワツクス
エマルジヨンを耐水性付与剤として使用して上記
のテストを繰返したが、硬化剤との相溶性が悪
く、接着剤エマルジヨンが製造できなかつた。[Table] Commercially available paraffin wax as a control test
The above test was repeated using the emulsion as a water resistance imparting agent, but the adhesive emulsion could not be produced due to poor compatibility with the curing agent.
Claims (1)
分をフリーデルクラフト型反応により重合して得
た軟化点常温〜150℃の樹脂、その樹脂のα・β
不飽和多塩基性酸付加物、又はパラフインワツク
ス、酸化パラフイン、マイクロクリスタリンワツ
クス、カルナバロウ、モンタンロウ、ポリエチレ
ンワツクスなる群から選ばれた少なくとも1種の
ワツクスに乳化剤を1〜15wt%使用し、予備乳
化を行つた後ピストン型高圧乳化機を用いて加圧
下で乳化を行うことを特徴とした硬化促進剤とし
て硫酸アンモニウムを含むホルムアルデヒド縮合
系接着剤用の耐水性付与剤の製造方法。1. A resin with a softening point of room temperature to 150°C obtained by polymerizing the -20 to 250°C fraction produced as a by-product during naphtha decomposition using a Friedel-Crafts type reaction, and α and β of the resin.
Using 1 to 15 wt% of an emulsifier in at least one wax selected from the group consisting of an unsaturated polybasic acid adduct, or paraffin wax, oxidized paraffin, microcrystalline wax, carnauba wax, montan wax, and polyethylene wax, A method for producing a water resistance imparting agent for a formaldehyde condensation adhesive containing ammonium sulfate as a curing accelerator, which comprises pre-emulsifying and then emulsifying under pressure using a piston-type high-pressure emulsifier.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP70282A JPH0238622B2 (en) | 1982-01-06 | 1982-01-06 | TAISUISEIFUYOZAINOSEIZOHOHO |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP70282A JPH0238622B2 (en) | 1982-01-06 | 1982-01-06 | TAISUISEIFUYOZAINOSEIZOHOHO |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58118874A JPS58118874A (en) | 1983-07-15 |
JPH0238622B2 true JPH0238622B2 (en) | 1990-08-31 |
Family
ID=11481096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP70282A Expired - Lifetime JPH0238622B2 (en) | 1982-01-06 | 1982-01-06 | TAISUISEIFUYOZAINOSEIZOHOHO |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0238622B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK1661951T3 (en) * | 2004-11-17 | 2011-02-14 | Romonta Gmbh | Process for preparing a montane wax derivative, a montane wax derivative and use of a montane wax derivative to prepare an aqueous montane wax compound |
-
1982
- 1982-01-06 JP JP70282A patent/JPH0238622B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS58118874A (en) | 1983-07-15 |
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