TW500758B - A process for producing an amino resin molding material - Google Patents

Abstract

This invention provider a process for producing an amino resin molding material, which is characterized by the use of water-soluble liquid amino resin containing more than 75% solid content and having at least one methylol group. The liquid amino resin is blended with other additives in a blender to form a blend in a semi-drying state, then the blend is directly subjected to a mixing step, to produce the amino resin molding material through a crosslinking reaction of the liquid amino resin. According to the present process, the drying step required by the conventional process could be eliminated without the use of the expensive and unworkable solid amino resin.

Description

500758 V. Description of the invention (1) [Technical background] Traditional amine-based resin molding materials are divided into two types, dry and wet. The dry method uses solid resin directly with fibrous materials such as paper and wood flour, and inorganic fillers, lubricants, accelerators, colorants and other components. In the solid (powder) dry state, it is directly crushed, mixed, kneaded, cooled, It is prepared by granulation or the like. As disclosed in Japanese Unexamined Patent Publication No. 6-571 00 and 7-1 1 850 1. The disadvantages are that the production of solid amine-based resins as raw materials is not easy, the price is high, and the resin may be hardened during the process, the softening point cannot be increased, and pollution and cleaning problems are likely to occur during powder transportation during the process. Wet powder and other fibrous materials, but also fillers, intermediate products, for example. This agent enhances the drying performance, and the solvent is added to produce the product, and the shellfish, j-dimensional materials, lubricants, granules, etc. are mixed with the additives. Although this process is added, it will be dissolved during the drying process. J It is not ideal to dry it by impregnating it with a solvent-containing liquid material, and then drying it with an accelerator, colorant, etc. Or add the above liquid special raw materials together with the steps of quick drying and kneading, etc. JP 59-189162, without using expensive solid drying steps to remove solvent residues in the resin; Furthermore, the latter part of the process can only be diluted after the solution is dissolved. It will also volatilize and contaminate the ring-shaped amine-based resin. It is then mixed with solid raw materials such as pulverized, mixed, bulk resin raw materials and high-speed mixers, and then cooled. Increased costs. Aldehydes and solvents will produce prone whitening and layering for impregnation and mixing, which will cause inorganic filling and kneading to the human body. It will be made of solid filled mixing granules. In view of such organic hazards, the inventors of the present invention have in-depth research on the relevant processes to find ways to improve

Chat 758 case number 88111235

5. Description of the invention (2) The method has thus completed the present invention [detailed description of the invention]], the purpose of the present invention is to provide ^ semi-dry manufacturing method of amine-based resin molding materials' This method does not require the use of organic solvents or drying Steps. The method for preparing the amine-based resin molding material provided by the present invention is used alone = a water-soluble liquid amine-based resin having a content of more than 75% and containing at least one hydroxyformamidine or used in combination with other self-hardening resins in a semi-dry state After the heating and kneading step with the other additives, the liquid amine-based resin can be polymerized into an amine-based resin molding material with a relatively large molecular weight to complete the present invention. The method of the present invention ϊ ΐ: the advantages of dry and wet methods and eliminate their disadvantages, and the traditional wet; produce = and: the method can omit the drying step can also avoid the process of odorless solvents, and can solve the dry method In the production method and the rotation cleaning caused by the powder, it is necessary to avoid the use of organic solvents in the powder flying, which means that it has the utility of environmental protection and environmental protection. -Each methyl group has a solid content higher than m and contains at least a resin. Use it together: 机: organic: amine: fat or other self-hardening materials that will not agglomerate and slip! , Promoting agents: colorants, etc .... Dry and bulk amine-based resins are crosslinked and made. After that, the liquid is mixed into powder or granules by heating and kneading steps. 2 Liquid amine-based resins such as melamine and other amine-based compounds used in the Ming Dynasty are prepared separately by adding urea, ζ η 彳, formaldehyde or its derivatives in the presence of urea and a second catalyst. Urea formate

500758 V. Description of the invention (3) ---- Amino resins such as grease, melamine formaldehyde resin and melamine phenol formaldehyde resin. In this reaction, the ratio of the amine compound to formaldehyde and its derivatives needs to be controlled at a molar ratio of F / M of the formaldehyde or formaldehyde derivative (represented below) to the amine compound (= represented by M) above u. More formaldehyde (F) can be used as bridging agent than urea or melamine (M) to produce cross-linking hardening. The F / M of the five applications may be in the range of 1.0 to 6.0, and preferably ι · 0 to 2.5. The amine-based resin molding material prepared by the manufacturing method of the present invention has the fluidity and heat distortion temperature of the finished product compared to those made by conventional methods, and the values are 80 to 95 cm and 180 to 200 ° C, respectively. The catalyst used may be, for example, alkali metals of Groups I and π in the periodic table, oxides or hydroxides of earth test metals or aqueous ammonia and other basic substances of amines. The above catalysts can be used singly or in combination of two or more kinds, and the addition amount thereof is preferably 5% to the total weight of the reactants. The reaction temperature can be in the range of 50 ° C to 100 ° C. This reaction process is mainly to obtain a water-soluble amine-based resin. Therefore, when the gelation time (Ge 1 Time) of the reactant reaches a predetermined target, it is dried under reduced pressure to Stop the reaction, and adjust the degree of drying to control the moisture content according to the content of the desired solid content, so that the content of the solid content reaches 50% or more, preferably 75% or more, that is, the product is water-soluble and contains at least one methylol group. For liquid amine-based resins, the degree of dehydration is controlled at a solid content of 75% or higher. Gelation time is based on the method of J IS K6909. If the above liquid amine-based resin continues to react to a specific molecular weight in the reflux reaction stage, it is then dehydrated under reduced pressure, and evacuated to a specific softening point or gelation time below 1000 ° C to release the solid amine after rapid cooling. Based resin.

A: \ 15785.ptd Page 6 刈 0758 V. Description of the invention (4) The amine-based wax molding material of the present invention is the German envoy ^-Case No. 88111235 April 4, n Supplementary to the above method, -Η Η W π 1% / private liquid amine-based resin can be mixed with other phenolic resins or thermosetting resins and / or other additives in a semi-dry manner. That is, the aforementioned resins and paper, wood flour fiber material, inorganic filling materials, lubricants, j-colors, etc. are uniformly stirred and mixed in a kneading machine, a ball mill, a drum, a rapid mixer and the like After that, it is discharged into the drum machine or extruded with single or double shafts. In this step, under the heating state of 60 to i4 (rc temperature), the moisture content is controlled by 绫 $ L ^ lice to achieve the specifications of the finished product. =. ^ To 15 to 4 generations and crushed into granules or powder with a pulverizer to obtain the amine-based resin molding material of the present invention. The amount of fenjun tree wax or thermosetting resin used is equal to ίϋί! "Add one half of the amount, and it must be able to make the formula in the formula :: keep in the semi-dry type, will not cause agglomeration or affect the operability of the original shellfish, the ingredients of the tree wax used The molar fraction of the reaction is the sum of the molar fraction of the reaction = the weight of the total wax of the amine-based resin. The F / M molar ratio of the reaction + the weight of the resin.% By weight. Topology ΐ The total F / M molar ratio of the total resin 2 Λ (the sum of the F / M molar ratio of the thermal resin). Paper and wood flour fiber weight% or more can pass through 80 # sieve are each good. Paper and wood flour fiber material addition: ί Jia, 95 weight% or more, 25% to 75% range. '丨 is the oxygen of the amine-based resin. The compounds used in the present invention (such as magnesium oxide, inorganic filling oxidation, materials including metal oxides or hydroxides, oxidizing bell, oxidation

2001.01 04. 008 500758 V. Description of the invention (5) ------ Ming, aluminum hydroxide, magnesium hydroxide, etc.), metal carbonates (such as: carbonate, calcium carbonate, carbonate, etc.), metal sulfates And sulfides (· 2, barium sulfate, sulfide, etc.), metal silicates (for example: acidic acid,: acid, etc.), stone compounds (for example: oxidized stone, oxidized oxide, carbonized stone) Etc.) 'mineral powder (for example: emery, corundum powder, talc powder, celite, kaolin, silica, etc.), or glass fiber (the ratio of the length of glass fiber L to the diameter of glass fiber D is L / D = The range is less than 5000), etc., and the addition ratio of the inorganic filler is in the range of U to 50% by weight of the amine resin. '' The lubricants used in the present invention include fatty lubricants (eg, stearic acid, stearic acid, magnesium stearate, calcium stearate, butyl stearate, etc.), fatty ammonium lubricant Agents (eg: saturated or unsaturated monoammonium type lubricants such as dodecylamine, myristylamine, oleylamine, stearylamine, and saturated or unsaturated dioleamide, distearylamine, etc. Saturated stilbene-based lubricants), alcohol-based lubricants (eg: PEG400, PEG1000, higher alcohols, etc.), paraffin-based lubricants ^ are mainly straight-chain hydrocarbons containing 28 to 90 carbons, for example: Liquid butterfly, paraffin wax, petroleum wax (Paraffin Wax), Sasol Wax (Sasol Wax, etc.) and silicone-containing lubricants (such as: silicone oil, etc.), the additive ratio of the lubricant is 0.1% by weight of the amine-based resin To the 20% range. The accelerators used in the present invention include inorganic acid-based accelerators (eg, sulfuric acid, boric acid, phosphoric acid, hydrochloric acid, etc.), and organic acid-based accelerators (eg, oxalic acid, benzoic acid, diacid if, p-toluene, etc.) Acids, etc.), organic amine salt-based accelerators (the salts of the aforementioned acids with triethanolamine, triethylamine, 2-methyl-2-amino-1-propanol, etc., for example: CATANITT〇, CATANITTO- A, etc.), inorganic metal salt-based accelerators (such as ...

A: \ 15785.ptd Page 8 500758 -is_8mi235

fo AA m, invention description (6) L ——————, etc.), etc., the addition ratio of the accelerator is in the range of 20% by weight of the amine resin. Fifth, the following examples, formulation examples and comparative examples are listed to explain the present invention in more detail, but the present invention is not limited thereto. The softening points in the examples were determined by the ring and ball method. In this method, a ring is placed on a glass sheet covered with a thin sheet of paper to heat, and a 20 g sample is dared to be stored in the ring. After the sample is warmed up and the sample is melted, the ring is placed on a ring frame and cooled for 20 minutes. Place it in the center of the test piece and move to a water bath to heat up at a rate of 5 ± 0'5 ° C per minute. Read the sample to start softening. The degree of overflow when the steel ball falls 25.4 mm is the softening temperature. The gelation time was measured at 150 ° C. In addition, "parts" in the examples, formulation examples, and comparative examples are all parts by weight. [Examples] Example 1 2,000 g of a 37% methyl butyrate aqueous solution, 15 g of a 10% sodium hydroxide aqueous solution, and 1,850 g of melamine were charged. Put it into a flask and heat the reaction at 80 ° C for 2 hours, then dry it under reduced pressure to obtain a solid content of 85% and a gelation time of 6 to 7 minutes, about 25Q0 grams of melamine-formaldehyde resin. Compound Jfe Example 2 2. The reaction was carried out according to the same formula and method of Example 1, but after the reaction was completed, it was dried under reduced pressure at 90 ° C. to obtain a softening point of 90 π and a gelation time of about 2 to 100 minutes of solid melamine— Formaldehyde resin. Column 3: 2000 grams of 37% aqueous formaldehyde solution, 10 grams of 28% ammonia solution, and 1500 grams of melamine were charged into the baking, and heated under reflux at 100 ec.

15785.ptc Page 9 2001 · 04.04 · 010 500758 V. Description of the invention (7) After 2 hours, it should be dried under reduced pressure to obtain a solid content of 85% and a gelation time of 5 to 6 minutes. About 2400 grams of melamine-formaldehyde resin. Example 4 20,000 g of a 37% aqueous formaldehyde solution, 40 g of hexamethylenetetramine, and 1100 g of urea were charged into a flask, and the reaction was heated under reflux at 500 c for 100 minutes and dried under reduced pressure. Approximately 1,800 grams of urea-formaldehyde resin with a solids content of 85% and a gelation time of 5 to 6 minutes. Example 5 680 grams of phenol, 600 grams of a 37% aqueous solution of acetaldehyde, and 15 grams of a 10/0 sodium hydroxide aqueous solution were charged into a flask, and the mixture was heated under reflux at 80 t for 60 minutes, and then cooled to 45 ° C. Add 1 900 grams of 37% aqueous formaldehyde solution and 2000 grams of melamine at 85. (: Heated under reflux for 60 minutes, then neutralized with 10 grams of 10% aqueous sodium hydroxide solution, and then dried under reduced pressure to obtain a solid content of 85%, gelation time of about 2000 grams of melamine-phenol-formaldehyde 4 minutes 30 seconds Resin. Example 6 The reaction was performed according to the same formula and method as in Example 5, but after the reaction was completed, it was dried under reduced pressure at 90 ° C to obtain a softening point of 90 ° C and a gelation time of 2 minutes 30 seconds to 3 minutes. Approximately 1,700 grams of solid melamine-phenol-formaldehyde resin in 30 seconds. Example 7 A flask was charged with 940 grams of phenol, 2000 grams of a 37% aqueous formaldehyde solution, and 5 grams of a 50% aqueous sodium hydroxide solution. The reaction was heated at reflux at 60 ° C for 60 minutes, then dried under reduced pressure and neutralized by adding 1.8 g of acetic acid.

A: \ 15785.ptd Page 10 500758 V. Description of the invention (8) Continue drying under reduced pressure at V to obtain a softening point of 80V and a gelation time of about 1 700 grams of solid phenol-formaldehyde resin at 60 to 70 seconds. . [Formulation example of amine-based resin molding material] Formulation Example 1 100 parts of paper resin, 55 parts of talc, 15 parts of stearic acid, 3 parts of acetic anhydride, 1 part of titanium dioxide, 2 parts of the resin of Example 1 After mixing and mixing for 20 minutes, the wire is rolled into a drum machine and heated and kneaded. 5 After the kneading is completed, it is cooled with cold air and broken with a Speed Mill to obtain granular or powdered melamine-formaldehyde resin molding material. Formulation Example 2 Resin of Example 3 (solid content 75%) 70 parts of resin of Example 2 30 parts of paper powder 55 parts of talcum powder 15 parts of stearic acid 3 parts of dianhydride 1 part of titanium dioxide 2 parts of the same as in Formula Example 1 Method: A granular or powdered melamine-formaldehyde resin molding material is obtained.

A: \ 15785.ptd Page 11 500758 V. Description of the invention (9) Formulation example 3 Resin of Example 3 (solid content 75%) 100 parts of wood powder 55 parts of talcum powder 15 parts of zinc stearate 3 parts of acetic anhydride 1 2 parts of titanium dioxide According to the same method as in Formula Example 1, granulated or powdered melamine-formic acid resin molding material was obtained. Formulation Example 4 The resin of Example 4 (solid content 75%) 100 parts of paper powder 50 parts of talcum powder 10 parts of stearate 3 parts of magnesium stearate 1 part of acetic anhydride 0.5 part of titanium dioxide 1 part of Formula Example 1 In the same way, a granular or powdery urea-formaldehyde resin molding material is obtained. Formulation Example 5 70 parts of resin of Example 4 30 parts of resin of Example 2 Wood powder 55 parts Talcum powder 15 parts

A: \ 15785.ptd Page 12 500758 V. Description of the invention (ίο) Zinc stearate 3 parts Magnesium stearate 1 part Magnetic anhydride 0.8 parts Titanium dioxide 1 part According to the same method as in Formula Example 1, obtain a granular or Powdered Urea-Melamine-Formaldehyde Resin Molding Material Formulation Example 6 The resin of Example 5 100 parts of paper powder 55 parts of talcum powder 15 parts of zinc stearate 3 parts of sulfurous acid 3 parts of titanium dioxide 2 parts The same as in Formula Example 1 Method, to obtain granular or powdered melamine-isocyanate resin molding material. Formulation Example 7 Resin of Example 1 (solid content 75%) 70 parts of resin of Example 6 30 parts of paper powder 55 parts of talcum powder 15 parts of zinc stearate 3 parts of sulfite 3 parts of titanium dioxide 2 parts < according to the formulation example 1 the same way to obtain granular or powdery & /

A: \ 15785.ptd Page 13 500758 V. Description of the invention (11) Melamine-phenol-formaldehyde resin molding material. Formulation Example 8 Resin of Example 3 (solid content 75%) 70 parts of resin of Example 7 30 parts of paper powder 5 5 parts of talc 1 5 parts of zinc stearate 3 parts of zinc sulfite 3 parts of dioxin 2 parts According to the same method as in Formulation Example 1, a granular or powdered melamine-phenol-formaldehyde resin molding material was obtained. Comparative Example 1 100 parts 5 5 parts of the resin paper powder of Example 2 15 parts 3 parts 1 part 2 parts talc powder zinc stearate gallate anhydride titanium dioxide, the above raw materials were mixed in a ball mill for 6 to 8 hours and then 'drained into a roller' Machine, guilty, according to the same method as in Formula Example 1, a granular or powdered melamine-brewed resin molding material was obtained. Comparative Example 2 According to the reaction method of Example 1, water was produced to obtain a solid content of 60%, but the conditions for drying under reduced pressure were changed to control the resin, and 100 parts of the resin was added.

A: \ 15785.ptd Page U 500758 V. Description of the invention (12) 25 parts of pulp are kneaded with a kneader for 50 minutes and then dried in an oven at 90 ° C for 2 hours' to obtain a dried product a. Dried product A 150 parts talc powder 15 parts zinc stearate 3 parts tartaric anhydride 1 part titanium dioxide 2 parts After mixing the above raw materials in a ball mill for 6 to 8 hours, a powdered melamine-formaldehyde resin molding material can be obtained, or Drain into the drum machine and knead, and then according to the same method of Formula Example 1, acid resin molding material. Comparative Example 3 Granular melamine-formaldehyde was obtained. According to the reaction method of Example 1, but changing the conditions for drying under reduced pressure to control moisture, a resin having a solid content of 50% was obtained. 25 parts of pulp was added to 100 parts of the resin. 'After kneading with a kneader for $ q minutes, it was dried in an oven at 90 ° C for 2 hours to prepare a dried product b. Dried product B 150 parts zinc stearate 3 parts acetic anhydride 0 · 5 parts titanium dioxide 2 parts After mixing the above raw materials in a ball mill for 6 to 8 hours, powdered urea ~ formaldehyde resin molding material can be obtained; or leaked into the drum machine After kneading, and according to the same method as in Formula Example 1, granular urea-formaldehyde resin molding material can be obtained.

A: \ 15785.ptd Page 15 500758 V. Description of the invention (13) Comparative Example 4 The resin of Example 6 100 parts of paper powder 55 parts of talcum powder 15 parts of zinc stearate 3 parts of zinc sulfite 3 parts of dioxin 2 After mixing the above raw materials in a ball mill for 6 to 8 hours, the mixture was discharged into a drum machine and kneaded. Then, according to the same method as in Formula Example 1, a granular melamine-phenol-formaldehyde resin molding material was obtained. Comparative Example 5 A resin having a solid content of 50% was obtained according to the reaction method of Example 5 but changing the conditions for drying under reduced pressure to control moisture. 25 parts of pulp was added to 100 parts of the resin and kneaded by a kneader 5 After 0 minutes, it was dried in an oven for 2 hours to obtain a dried product c. 1 50 parts 15 parts dry matter C talcum powder 3 parts 3 parts 2 parts stearate zinc sulfite zinc oxide The above raw materials are mixed in a ball mill for 6 to 8 hours, and then drained into a drum machine for kneading, according to the formula example 丨In the same way, a granular melamine-phenol-formaldehyde resin molding material was obtained. The properties of the finished products obtained in Formulation Examples 1 to 8 and Comparative Examples are shown in Table 1.

A: \ 15785.ptd Page 16 500758 _ Case No. 88111235_ Qin Zhengwu on April 4th, the description of the invention (14) 一一 —u ... From Table 1, we can know that the method of the present invention is based on liquid amine resin. The formulated amine-based resin molding materials are not inferior to the traditional ones in the characteristics of the finished products (Comparative Examples 1 to 5), and even better than the traditional winter molding materials in terms of fluidity and heat distortion temperature of the finished products. It can be seen from this that the forming material of the present invention is indeed progressive, and has advantages in terms of cost and environment in the manufacturing process. Table 1 Comparison of the characteristics of the finished product Melamine-methacrylic resin surface material urea- (melamine) -formaldehyde resin molding material melamine-phenol-formaldehyde resin molding material Special Example 1 _ 2 Example 3 Leg example 1 t-dagger example 2 W5 example 4 WJJ example 5 臓 example 3 15 ^ example 6 EJj tribute example 7 recipe. Example 3 leg example 4 dirty example 5 §i3i7 (^ spiral flow) (cm) * 80 85 85 80 75 85 85 80 85 80 85 80 75 75 ( Chappy Strength) (kg-Xcm / cm Xcm) 4.0 4.2 4.2 4.2 3.8 4.0 3.8 '4.0 4.0 4.2 4.0 4.2 4.0 (Flexural Strength) (kg / mm Xxrtrn) 10 9.5 10 10 9 10 10 11 10 10 10 10 10.5 OcV / mm) Dieleoric Strength 10 10 10 10 11 10 10 11 10 10.5 10.5 10 11 13Il (sec) Arc Resistance 140 140 1S0 180 140 120 120 120 180 180 140 180 180 Ig ^^ OhsuIation Resistance ( Ν) Ε10 × Ω 60 40 60 20 60 60 1C0 1C0 60 50 60 20 • 20 Heat Resistance 150 150 150 150 150 120 130 120 140 140 150 140 140 (Deflection Temp) 185 180 185 175 165 120 130 120 185 180 1S5 170 165 * Flowability test conditions are 155flc X 100kg / cni2 X 4 (3g material according to J IS K6911 method test 11 ^ 1 — 15785, ptc page 17 2001 * 04 · 04’018

Claims (1)

758 Amended j 丨 Μλ f zzzM Patent application scope Six methods of manufacturing an amine-based resin molding material, which are characterized by using a water-soluble liquid amine-based resin with a solid content of more than 75% and containing at least one methylol group, in addition to Huata Solid or liquid self-hardening resin, in a semi-dry state, directly mixed with other additives at a temperature of 60 to 140 t, kneaded, and cooled to 15 to 4 (TC after granulation;… wherein the other solid or liquid The total amount of the hard resin and the liquid amine-based resin containing at least one methylol group accounts for 20 to 70% by weight of all the ingredients. &Quot; " The base resin is selected from urea, melamine-based amine-based compounds or derivatives thereof, aldehyde formaldehyde or derivatives thereof, and is used in a range of formaldehyde / amine-based F / M mole ratio ^ 1.0 to 6 · G. Alkali or alkaline earth metal oxides or hydroxides or ammonia and other amine alkaline substances are used as catalysts. 3. For example, the method of making a patent application scope item 1, wherein the additive is paper, wood flour fiber material Inorganic filling materials, lubricants, and accelerators. 4. According to the manufacturing method of item 丨, the amount of the other solid or liquid self-hardening resin is 10 to 50 of the amine-based resin containing at least one methylol group. 5. The production method according to item 3 of the patent application, wherein the additive contains 80% to 95% by weight of particles that can pass through 80 # sieve, and 25 to 75% by weight of the resin is added. % .... Amine 6. The production method according to item 3 of the scope of patent application, wherein the inorganic filling material is selected from the group consisting of metal oxides and hydroxides, metal carbonates, and metal sulfuric acid ', 15785.ptc 2001 · 04 · 〇4 · 〇19) υυ758 88111235 Seven-year amendment application patent " " ^^--honey or sulfide, metal silicate and silicide, mineral powder and slope fiber: its The amount added is 1 to 50% by weight based on the weight of the amine-based resin. For example, the manufacturing method of item 3 of the patent scope, wherein the lubricant is a fat agent, a fatty ammonium-based lubricant, an alcohol-based lubricant, and a paraffin-based lubricant, and the added amount is an amine group. Resin weight is 20% by weight. · 1% by weight to ^ method of patent application 3 items, wherein the accelerating accelerator 'organic acid accelerator, inorganic acid organic metal salt accelerator, the addition ratio =; = agent, no 0.01 to 20 weight %By. 】 Mamine & Tree Known Weight 9. A fluidity and 180-200 ° C bismuth produced from the amine-based resin molding material as described in the patent application No. p is a heat distortion temperature of the finished product L having 80 to 95 cm. 2001 · 04 · 04 · 020