JP2002524634A - Resin curing method - Google Patents

Abstract

  (57) [Summary] PROBLEM TO BE SOLVED: To provide a method of curing a resin which can start curing at a desired time. A method of manufacturing a product having at least two parts, at least partially coating one of the parts with a resin encapsulating a catalyst therein, and placing the part with the resin therebetween. And starting the curing of the resin at a desired time by releasing the catalyst into the resin. The catalyst may be encapsulated by encapsulation or adsorbed on a suitable substrate structure, such as tonsil epidermis. As the catalyst, an organic peroxide, formic acid or toluenesulfonic acid can be used. Accelerators can be used to accelerate curing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method for controlling the curing of a resin and to an improved resin capable of such control. The invention also includes applications relating to methods and uses of curing resins in the production of articles.

[0002]

[Prior art]

In the production of plywood, for example, each layer of wood is coated with a resin, pressure is applied integrally, and heating is performed to cure the resin.

[0003]

[Problems to be solved by the invention]

The time until heat is supplied and hardening is considered to be a stagnation of the processing step. The curing time can be shortened by mixing the catalyst with the resin, but since the curing may start before or during the application of the resin, such a method may hinder the processing step itself .

[0004]

[Means for Solving the Problems]

According to one aspect of the present invention, a step of confining (trapping) a catalyst that starts curing when released to a resin, a step of mixing the catalyst with the resin, and a step of releasing the catalyst to the resin to cure at a desired time Starting the resin.

In accordance with another aspect of the present invention, there is provided a method of making a product comprising at least two parts, the method comprising at least partially encapsulating a catalyst encapsulating one of the parts with a resin distributed therein. Coating, placing said portion with said resin therebetween, and releasing said catalyst to said resin to initiate curing at a desired time.

The present invention also includes a resin produced by the above method and a resin to which the catalyst used in the method is distributed.

The catalyst may either be hardened by encapsulation or adsorbed on a suitable substrate structure, such as the almond shell.

[0008] The resin may be any of a polyester resin, a vinyl ester resin, a phenol formaldehyde resin, an epoxy resin, an acrylic resin, a melamine / urea formaldehyde resin, and a phenol resin.

As the catalyst, for example, any of the following appropriate ones may be used. That is, organic peracid
Compounds : For example, dibenzoyl peroxide, methyl ethyl keto peroxide, cumene hydroperoxide, acetylacetone peroxide (commercially available under the trade name of Triggernox 44B), tert-butylperoxybenzoate (commercially available under the trade name of Triggernox C) ), Tert-butyl-2-ethylhexanoet (commercially available under the trade name Triggernox 21), tert-butylperoxy-3,
5, 5, trimethylhexanoet (commercially available under the trade name of Toganox 42s), cumene hydroperoxide (commercially available under the trade name of Triggernox K-80),
A suitable catalyst such as Biz (4-tert-butylcyclohexylperoxydicarbonate) (commercially available under the trade name Percadox 16). Amine catalysts : for example, diethyltetraamine, triethylamine isocyanate, boron trifluoride, ultraviolet curing catalysts , alkyl carbonates : for example, propylene and ethylene carbonate, and minerals and organic acids such as formic acid, toluenesulfonic acid or Sulfuric acid.

As the encapsulating agent, any of the following can be used. That is, gelatin, thermosetting resins, fats, waxes, thermoplastics, cured compounds, or silane compounds or WO 98/9898 in the international application filed by the present applicant.
No. 26865 is an encapsulating agent.

Hardening accelerators such as cobalt octoate (commercially available under the trade name NL-49-P), diethylaniline (commercially available under the trade name NL-64-10P), amonium sulfate or amonium chloride are also available. Can be used. The size of the encapsulated or coated particles is between 0.5 and 1000 microns.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

 Embodiments of the present invention will be described below by way of examples.

The first embodiment is an invention relating to the production of a wood plywood material layer, in which a resin is sandwiched between adjacent plywood layers, pressure is applied integrally, and heat is applied to promote hardening. The resin has a strong wood layer and sticks together. In the conventional process, pressure and heat are applied for a considerable time. For example, application of pressure and heat for several minutes increases production time and cost. According to the invention, the catalyst distributes through the resin. As the catalyst, a suitable catalyst such as propylene carbonate, ethylene carbonate or the like can be used, and the catalyst initiates the curing of the resin causing the bonding between the adjacent layers of the wood. However, premature curing or premature curing may make it difficult or impossible to perform the manufacturing process satisfactorily or efficiently. For example, when coating a plywood layer with a resin, if the curing has already progressed, it is not easy to coat the plywood layer with the resin, and even if the resin can be wetted, the bond strength between the plywood layers is reversed. Will be affected.

To overcome this possible disadvantage, the release of the catalyst into the resin that initiates curing can be controlled by encapsulating the catalyst. Encapsulation is achieved by exposing the catalyst to ultrasound in the presence of the encapsulating agent to produce microcapsules of the catalyst coated with the encapsulating agent. Even though the encapsulated catalyst capsule is distributed through the resin, the coating separates the catalyst from the resin. In this state, the resin can be coated on the layer of wood as described above, but curing does not begin and does not affect this processing step until the granules rupture and release the catalyst to the resin. Bursting can be caused by exposing the granules to ultrasound or heating or other suitable method.

[0015] In another method of encapsulation, the catalyst is first adsorbed on the surface of the granules of inert material and then exposed to ultrasound and again coated with a hardener. In each case, the size of the coated particles generally ranges from 0.5 to 1000 microns.

As the catalyst, for example, any of the following appropriate ones may be used. That is, organic peracid
Compounds : dibenzoyl peroxide, methyl ethyl ketopoxide,
Cumene hydroperoxide, acetylacetone peroxide (commercially available under the trade name Triggernox 44B), tert-butylperoxybenzoate (commercially available under the trade name Triggernox C), tert-butyl-2-ethylhexano Eto (
Commercially available under the trade name Trigger Knox 21), tert-butyl peroxy-3,5
, 5, trimethylhexanoet (commercially available under the trade name of Toganox 42s), cumene hydroperoxide (commercially available under the trade name of Triggernox K-80), Biz (4-tert-butylcyclohexylperoxydicarbonate) ( (Available under the trade name of Percadox 16). Amine catalysts : for example, diethyltetraamine, triethylamine isocyanate, boron trifluoride, ultraviolet curing catalysts , alkyl carbonates : for example, propylene and ethylene carbonate, and minerals and organic acids such as formic acid, toluenesulfonic acid or It is sulfuric acid.

The curing accelerator is cobalt octoate (commercially available under the trade name NL-49-P)
, Diethylaniline (commercially available under the trade name NL-46-10P) can be used.

The encapsulant may be any of the following or a mixture thereof: That is, a gelatin, a thermosetting resin, a fat, a wax, a thermoplastic substance, a cured compound, a silane compound, or a curing agent described in International Publication No. WO98 / 26865 filed by the present applicant. .

The resin may be any of the following or a mixture thereof. That is, polyester resin, vinyl ester resin, phenol formaldehyde resin, epoxy resin, acrylic resin, melamine / urea formaldehyde resin, and phenol resin.

In a second embodiment, the catalyst is confined by absorbing the catalyst into a suitable substrate, rather than by the above-described adsorption method. A suitable substrate is the tonsil epidermis, which has a surface that promotes adsorption and absorption of the catalyst. For example, other catalysts and resins described in detail above can be used, but formic acid is used as the catalyst and melamine / urea formaldehyde resin is used as the resin.

The method for producing the tonsil epidermal formic acid / toluenesulfonic acid catalyst material is as follows. 1) First, formic acid / toluenesulfonic acid is dissolved and distributed in acetone. Acetone acts as a carrier solvent that leads into the acid-catalyzed tonsil epidermal porous structure. 2) The tonsil epidermis is then added to the acid / acetone mixture. 3) The acid / acetone / tonsil epidermis mixture is sonicated for 3-5 minutes using a 400 kHz ultrasonic probe at 20 kHz until the acetone / acid is adsorbed and absorbed by the epidermis structure of the tonsil. This step is more easily observed than the rather thick appearance of the mixture. One of the reasons for the use of solvents is that ultrasound works effectively in very hard tonsil epidermal concentrations. Excess liquid (ie, acetone) where cavitation can develop is needed. The collapse of the cavitation bubbles creates a large source of energy / shock waves that carry the liquid mixture into the epidermis of the tonsil. 4) The acetone solvent is removed from the slurry mixture using a drying method, leaving only the acid catalyst implanted on the tonsil epidermis. The acetone is removed and the acetone is recycled using a condenser. The tonsil epidermis / acid catalyst product is a fairly free flowing powder that can be relatively easily dispersed in the resin.

Acetone is used as a solvent because: a) Acetone has very good solubility. For example, paratoluenesulfonate catalyst (PTSA) is a solid powder that must be dissolved in acetone before being transported to the tonsil epidermis. B) Acetone has a low boiling point. That is, its removal is promoted during the drying process at a low temperature. This is a very important property when formic acid is used. This is because the catalyst has a relatively low boiling point, and therefore formic acid is also removed when a high drying temperature is used, and c) the presence of acetone in the sonication step reduces the temperature. It can be kept very low (specific heat capacity characteristic) to reduce or eliminate evaporation problems.

When the tonsil epidermis / acid catalyst is dispersed in the resin, it is not possible to access the tonsil epidermis structure so easily or quickly because the resin molecules are so large. Therefore, the resin cannot be brought into contact with the acid catalyst fixed on the surface of the skin structure. Therefore, curing of the resin does not start. The acid catalyst is activated by heat. This expands and opens the structure, allowing the resin to obtain the catalyst. Note that this is not a technique of encapsulation, nor is it coated.
However, the coating could be applied if longer-term stability is required in the end user / application.

Although the present invention has been described with reference to the above embodiment, it goes without saying that implementation and many modifications are possible without departing from the spirit of the present invention. For example,
The method of the present invention comprises coating one or more parts with a curable resin and / or
Or it is applicable to the manufacture of any product which can be saturated and said parts can be supplied together or be part of a production process.

The felt or glass fiber can be filled with the curable resin of the present invention, molded into a desired shape, and cured. The material may be supplied pre-saturated with the resin for use downstream of the manufacturing process. These material compositions could be used in the following general fields: 1) Construction of boats 2) Automobile industry, for example, internal and external parts and body panels 3) Construction of trains and airplanes, for example, internal and external parts and body panels 4) Application to offshore offshore oil field drills 5) Building construction-wall panels (inside / outside), roofs 6) Household goods 7) Surface coatings 8) Fire resistant foams / coatings / compositions 9) Paint and paper industry binders 10) Foundry industry binders 11) Filaments Winding 12) Extrusion of plastics 13) Adhesives 14) Boards of MDF / particles 15) Fabric molding formulations 16) Pre-saturated products 17) Binders for concrete applications used in the building / construction industry

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] September 20, 2000 (2000.9.20)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 11/00 C09J 11/00 201/00 201/00 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZWF terms (reference) 4F070 AA29 AA44 AA45 AA46 AA47 AA63 AC19 AC20 AC35 AC40 AC42 AC46 AC50 AC56 AC65 AD05 AD06 AE08 FA14 FB02 GB09 4J002 AE051 BG001 CC001 CD001 CF001 DF007 DG046 DG047 EF036 EG047 EH006 EK006 EK026 EK046 EK066 EK076 EK086 EN046 EN067 EV236 FB266 FB286 FB296 FD146 FD157 GC00 GF00 GH 001 GL00 GN00 4J040 BA162 BA172 BA182 DE051 EF111 EB001 EB001 EB001 EB001 JB08 KA05 KA12 KA 13 KA14 MA08 MB05 NA13 PA32

Claims (16)

[Claims] 1. A step of confining a catalyst which starts curing of the resin when released into the resin, a step of mixing the trapped catalyst with the resin, and a step of releasing the catalyst into the resin to start curing. A method for curing a resin, comprising: 2. A method of producing a product comprising at least two parts, wherein at least one of said parts is at least partially coated with a resin having a trapped catalyst distributed therein, and said part is made of said resin. And intervening therewith, and releasing the catalyst to the resin to initiate curing at a desired time. 3. The method according to claim 1, wherein the catalyst is encapsulated by encapsulation. 4. The method according to claim 3, wherein the material used for encapsulation is gelatin, thermosetting resin, fat, wax, thermoplastic, hardened compound, silane compound, or applied by the present applicant. International Publication No. WO9
A method comprising one or more of the encapsulating agents disclosed in Japanese Patent Application Publication No. 8/26865. 5. The method according to claim 1, wherein the catalyst is confined by adsorption and absorption. 6. The method according to claim 5, wherein the catalyst is confined by adsorption to the tonsil epidermis. 7. The method according to claim 1, wherein the resin is a polyester resin, a vinyl ester resin, a phenol formaldehyde resin, an epoxy resin, an acrylic resin, melamine / urea formaldehyde. resin,
A method comprising one or more of phenolic resins. 8. The method according to claim 1, wherein the catalyst is an organic peroxide. 9. The method according to claim 1, wherein the catalyst is dibenzoyl peroxide, methyl ethyl ketopoxide, cumene hydroperoxide, acetylacetone peroxide as an organic peroxide. (Commercially available under the trade name of Triggernox 44B), tert-butyl peroxybenzoate (commercially available under the trade name of Triggernox C), tert-butyl-2-ethylhexanoet (commercial name of Triggernox 21) Tert-butylperoxy-3,5,5, trimethylhexanoet (commercially available under the trade name of Toganox 42s), cumene hydroperoxide (commercially available under the trade name of Triggernox K-80) Or Biz (4-tert-butylcyclohexylperoxydicarbonate) (a product of Percadox 16) In commercially available are), diethyl tetra amine as amine catalysts, triethylamine iso Saia sulfonates or boron trifluoride, ultraviolet
A method comprising one or more of a line curing catalyst, propylene and ethylene carbonate as alkyl carbonates , minerals and organic acids such as formic acid and toluenesulfonic acid, or sulfuric acid. 10. A step of dissolving formic acid in acetone, and the steps of:
A method of confining a formic acid catalyst in the tonsil epidermis, comprising the steps of: adding to the acetone mixture; and sonicating the mixture until the acetone and the mixture are also adsorbed and absorbed inside the epidermal structure of the tonsil. 11. The step of dissolving or dispersing toluenesulfonic acid in acetone, the step of adding tonsil epidermis to an acid / acetone mixture, and the step of dissolving or mixing the acetone acid mixture in the tonsil epidermis structure until it is adsorbed and absorbed. Sonicating the toluene sulfonic acid catalyst in the epidermis of tonsils. 12. The method of claim 10 or claim 11, wherein the acid / acetone mixture is sonicated with a 20 kilohertz, 400 watt ultrasonic probe for 3-5 minutes. 13. A process for confining a catalyst that starts curing when released to a resin, a process for mixing the confined catalyst with a resin, and a process for releasing the catalyst to the resin and starting curing at a desired time. 13. A method of curing a resin comprising: wherein the catalyst is confined by the method of claim 10, 11 or 12. 14. The method according to claim 1, wherein an accelerator is used to accelerate the curing. 15. The method of claim 14, wherein the promoter is cobalt octoate (commercially available under the trade name NL-49-P), diethyl aniline (N
L-64-10P), ammonium sulfate or ammonium chloride. 16. A product manufactured by the method according to claim 1. Description: