JPH1135699A - Production of product consisting of moisture curing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject product stably not requiring the blocking of a moisture during the production thereof or a specific humidity control by using a latent curing accelerator which is inactive in an initial state, but can be activated with some treatment. SOLUTION: This method for producing a product consisting of a moisture curing resin comprises performing three steps of (step 1) of mixing (A) a moisture curing resin (suitably a polyether having hydrolyzable silyl groups at both ends thereof, etc.), with (B) a latent curing accelerator for the component (A), (step 2) of activating the component (B) and (step 3) of blocking the composition containing the component (A) from the moisture. It is preferable to conduct the steps 1, 2 and 3 in this order, or conducting the process 1, and then conducting the step 3 immediately after conducting the step 2. As the component (B), e.g. a hardly soluble solid substance such as dibutlytin oxide capable of being activated by a heat treatment, is cited. It is preferable to perform the activation with a heat treatment at 40-180 deg.C. In order to block the moisture, it is preferable to contain the above composition in a hermetically closed container such as a can, a tube, etc., made of non moisture penetrable material such as a metal, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a product comprising a moisture-curable resin used as a paint, an adhesive, a sealant, a matrix resin of a composite material, and the like.

More specifically, in the production of a product made of a moisture-curable resin, there is no need for special moisture management such as completely avoiding contact with moisture in the production process or controlling the process to a very low humidity. The present invention relates to a method for producing a product made of a moisture-curable resin capable of producing a stable product.

[0003]

2. Description of the Related Art Room temperature curing resins used for paints, adhesives, sealants, matrix resins of composite materials, and the like include:
There are a two-pack type in which a main agent and a curing agent are mixed immediately before use, and a one-pack type comprising a moisture-curable resin.

The two-part room temperature curing resin requires time and effort to measure and mix the main agent and the curing agent, and also causes variability in the measurement and uneven mixing at the site, which causes the physical properties of the cured product to vary. It is difficult to handle, for example, it is easy to use, and the mixture needs to be used up in a short time.

On the other hand, one-part room temperature curing resins can be stably stored in a state where they are kept out of contact with moisture, and when exposed to the atmosphere, react with the moisture in the atmosphere and cure. As described above, the one-pack type room temperature curing resin is excellent in convenience such that mixing operation is unnecessary, the reproducibility of the physical properties of the cured product is good, and the remaining portion can be used for a long time if it is closed. However,
Products made of a one-pack type moisture-curable resin are easily cured when exposed to moisture. For this reason, it has been suggested that in manufacturing a product made of a moisture-curable resin, it is necessary to avoid contact with moisture as much as possible in order to prevent curing in the manufacturing process. For example, Japanese Patent Publication No. 61-608
No. 67, a method of manufacturing by completely shutting off moisture, and Japanese Patent Application Laid-Open No. 7-178728, a method of manufacturing in a very low humidity controlled environment of 10% or less relative humidity. And so on.

However, in such a manufacturing method,
There has been a problem that the manufacturing process becomes complicated, for example, an airtight container capable of blocking moisture is required, or a large-scale facility for maintaining the process at low humidity is required.

[0007]

SUMMARY OF THE INVENTION In view of the drawbacks of the prior art, the present invention does not provide a method for producing a product made of a moisture-curable resin, which does not require the shut-off of moisture during production and special humidity control. It is assumed that.

[0008]

The present invention employs the following means in order to solve the above problems. That is, the method for producing a product made of the moisture-curable resin of the present invention,
Mixing the moisture-curable resin (A) with the latent curing accelerator (B) of the resin (A) (step 1), activating the (B) (step 2), It is characterized by including three steps of a step (step 3) of substantially shielding the composition containing A) from moisture.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention has been made to solve the above-mentioned problems, namely,
After eagerly examining the method of manufacturing a product made of a moisture-curable resin without the need to block moisture during manufacturing or special humidity control, it is inactive in the initial state, but develops activity by some processing By using a latent curing accelerator, the problem was solved at once, and it was found that a product made of a moisture-curable resin could be stably manufactured even in a special low-humidity environment, and the present invention was completed. Things.

The technical point of the present invention will be described. In the present invention, the moisture-curable resin (A) including the step 1 is described.
In the compounding step and subsequent processing steps such as coating, since the latent curing accelerator is not activated,
Even if the moisture in the atmosphere is absorbed, the reaction between the moisture-curable resin and the moisture does not substantially occur. In the present invention, after the step 1, the product is manufactured through a combination step of the step 2 and the step 3. Specifically, the step 3 is performed immediately after the step 2 or the step 3 is performed. A method of performing Step 2 later is adopted.

In step 2 described above, by activating the latent curing agent, a reaction between the moisture absorbed so far and the moisture-curable resin occurs, and the absorbed moisture is consumed.
Even when the absorbed moisture reaches the saturated moisture amount, the amount is small compared to the number of functional groups involved in the crosslinking reaction of the moisture-curable resin, so that only a small part of the moisture-curable resin reacts It only needs to. At this stage, the moisture-curable resin composition is brought into an anhydrous state by consuming the absorbed water, and the latent curing accelerator is activated, so that the moisture-curable resin composition is cured by contact with moisture. In step 3, since the moisture-curable resin is shielded from external moisture, no further curing takes place, and a stable product can be manufactured.

The steps (steps 1 to 3) will be described in detail below. Step 1 of the present invention is a step of mixing the moisture-curable resin (A) used for the moisture-cured product and its latent curing accelerator (B). During this step, even if moisture is absorbed by contact with the atmosphere, the latent curing accelerator is in an inactive state, and the reaction between the moisture-curable resin and moisture does not occur. A controllable device need not be used, and any known mixing device can be used. Therefore, step 1 may be a batch type or a continuous type.

However, in step 1, it is necessary to select conditions that do not activate the latent curing accelerator. The conditions vary depending on the method of activating the latent curing accelerator to be used, for example, a method of heat treatment, light irradiation, electron beam irradiation, or the like. For example, in the case of a latent curing accelerator activated by heat treatment, care must be taken not to raise the temperature of the mixture above the activation temperature. In this case, it is necessary to take measures such as shielding from light or using a light source that does not include light having a wavelength to activate the latent curing accelerator, and furthermore, it is activated by electron beam irradiation. In the case of latent curing accelerators, care must be taken not to expose them to heat or light, since such agents are often unstable to heat or light.

Next, step 2 is a step of activating the latent curing accelerator. When the latent curing accelerator is activated, a curing reaction occurs between the moisture absorbed in the previous steps and the moisture-curable resin. However, immediately after or before the step 2, the moisture-curable resin composition (that is, the moisture-curable resin and the latent curing The moisture in the moisture-cured resin product can be reduced by combining step 3 as described above, even though the environment is in contact with atmospheric moisture, since the moisture in the composition comprising the accelerator is consumed and the water can be made anhydrous. Can be manufactured stably.

In step 2, the moisture-curable resin is partially cured by the moisture absorbed up to step 2.
However, the absorbed moisture is a fixed amount of moisture determined by the humidity history up to the step 2 and the type of moisture-curable resin,
Since the amount thereof is small compared to the number of functional groups involved in the crosslinking reaction of the moisture-curable resin, there is no problem if the moisture-curable resin component is designed in consideration of the partial curing here. In addition, a dehydrating agent described below can be previously blended. By these means, the viscosity, glass transition temperature, and the like of the moisture-curable resin composition (hereinafter, simply referred to as composition) can be controlled to desired values.

Various means can be used for activating the latent curing accelerator depending on the latent curing accelerator. For example, activation by heat treatment, activation by irradiation with light such as ultraviolet rays, activation by electron beam irradiation, activation by mechanical stimulation, and the like can be employed.

As a means for performing the heat treatment, any means can be used as long as the latent curing accelerator can be activated. However, electric heating, steam, infrared rays and the like can be preferably used. The temperature at which such heat treatment is performed is not particularly limited as long as the latent curing accelerator can be activated, but it is preferable to employ a latent curing accelerator that can be activated at 40 to 180 ° C. If the activation temperature is lower than this, the latent curing accelerator may be activated in the step before Step 2, and the moisture-curable resin may be cured. If the activation temperature is higher than this, there is a possibility that the moisture-curable resin may be altered.

When activation is performed by light irradiation,
It is necessary to select the wavelength of the light depending on the type of the latent curing accelerator, but it is generally preferable that the light having a wavelength in the range of 200 nm to 800 nm, more preferably 250 nm to 450 nm can be efficiently activated. Such light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, fluorescent lamps,
Lamps selected from chemical lamps, xenon lamps, halogen lamps and carbon arc lamps can be preferably used.

Next, when irradiating an electron beam, a usual electron beam irradiation apparatus can be used. Since this electron beam generally has a limited penetration depth, such an electron beam irradiation method is particularly preferably used for products made of a film-like moisture-curable resin.

As still another method, a method of applying a mechanical stimulus can be adopted.
Techniques such as applying a strong shearing force, applying a strong linear pressure, and irradiating an ultrasonic wave can be used.

Next, step 3 is a step of shielding the resin composition from moisture in order to prevent curing of the composition comprising the moisture-curable resin. As for such a blocking method, any method can be used as long as the composition composed of the moisture-curable resin can block moisture in the outside air, but it is made of a non-permeable material such as metal, glass, and plastic. It is preferable from a viewpoint of storage stability to put in a highly airtight container such as a case, a tube, a tank, a cartridge, or a bag. In order to further improve the storage stability, when sealing the container, dry air, nitrogen, a method of encapsulating a gas substantially free of moisture such as a rare gas into the container, or suctioning the air inside the package. For example, or a method of enclosing a desiccant such as silica gel or slaked lime in the container.

Next, the combination order of each step will be described. First, Step 1 is a step to be performed first. After Step 1, any order of Step 2 and Step 3 may be performed. However, when Step 3 is performed after Step 2, the composition From the viewpoint of preventing curing, it is preferable to perform Step 3 immediately after Step 2. In addition to the steps 2 and 3, it is also possible to add a step (molding step) of molding the composition comprising the moisture-curable resin into a desired form. Specifically, a step of applying a film on a substrate using a reverse roll coater, a kiss roll coater, a gravure coater, a knife coater, a bar coater, a slit die coater, an air doctor coater, a spray coater, a spin coater, or the like. And a step of impregnating the reinforcing fiber with a resin, a step of extruding from a die and forming into a film shape or a fibrous shape. These added molding steps are preferably performed between step 1 and step 3. When step 2 is performed before step 3, it is preferable to perform these molding steps before step 2, or to perform step 2 and the molding step simultaneously. When Step 2 and the molding step are performed at the same time, the shearing force and heat involved in the molding step can be used as a means for activating the latent curing accelerator.

Next, the moisture-curable resin (A) of the present invention and its latent curing accelerator (B) will be described. The moisture-curable resin (A) used in the present invention may be any resin that can be cured by reacting with moisture. The moisture-curable resin (A) may be used alone or in combination of two or more. Specific examples of preferred moisture-curable resins (A) include compounds having one or more hydrolyzable silyl groups in one molecule, compounds having two or more isocyanate groups in one molecule, and the like. A compound that reacts with water to increase the molecular weight can be used. In addition, a composition comprising an epoxy resin and a compound which reacts with water to generate an amine can be used.

First, the moisture-curable resin (A) comprising the compound having a hydrolyzable silyl group of the present invention will be described. The hydrolyzable silyl group referred to herein is a functional group in which a hydrolyzable group is bonded to a silicon atom represented by the following general formula (1), and forms a siloxane structure by a hydrolysis reaction to form a crosslinked structure. Is meant to be

X _n -Si (R ₁ ) _3-n- (1) (wherein, X is a hydrolyzable group, n is an integer of 1 to 3, and R ₁ is an alkyl group.) Specific examples include an alkoxy group, an acyloxy group, a ketoximate group, an alkyleneaminooxy group, an acylamino group, an aminooxy group, an alkenyloxy group and the like. When two or more hydrolyzable groups are bonded to one silicon atom, they may be the same or different. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms.

As such a compound containing a hydrolyzable silyl group, polyorganosiloxane having a hydrolyzable silyl group at a terminal and / or a side chain and polyether having a hydrolyzable silyl group at both terminals can be used. Specifically, for example, “Silyl” SAT20
0, SAT030, SAT010 (Kanebuchi Chemical Industry Co., Ltd.)
Exestar) ES-S3430, ES-S3
630, ES-S3620, ES-S3610, ES-
S2420, ES-S2410 (manufactured by Asahi Glass Co., Ltd.) and the like can be used.

As a method for producing such a compound having a hydrolyzable silyl group, a method of reacting an appropriate precursor with a silane compound having a hydrolyzable group, a method of reacting a precursor with a silane compound having an active functional group such as chlorine, or the like can be used. After reacting the compound, it can be produced by replacing the active functional group with a hydrolyzable group.

For the reaction between the precursor and the silane compound, various synthetic reactions can be used. One is a hydrosilylation reaction, in which a silane compound having a hydrogen silicon bond (eg, trimethoxysilane, trichlorosilane, etc.) is added to a compound having a plurality of unsaturated groups.

A method of reacting a functional group of a precursor with a functional group of a silane compound can also be used. For example,
A precursor having an epoxy group and an amino group, a mercapto group,
The reaction of a silane compound having a phenolic hydroxyl group or a carboxyl group, the reaction of a silane compound having an epoxy group with an amino group, a mercapto group, a precursor having a phenolic hydroxyl group or a carboxyl group, a compound having an isocyanate group and an amino group or a hydroxyl group The reaction of a silane compound having the same can be used.

Next, the moisture-curable resin (A) composed of the compound having an isocyanate group reacts with moisture in the presence of a curing accelerator to form a urea bond and cure. Such polyisocyanates include, for example, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,
For example, 4'-dicyclohexyl diisocyanate is preferably used.

A so-called urethane prepolymer having an isocyanate group at a molecular terminal obtained by reacting a polyol with these polyisocyanate compounds is also preferably used. At this time, as the polyol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, polyether polyol, polyester polyol and the like can be used.

Such polyether polyols include:
For example, a diol having a polyoxyethylene skeleton, a polyoxypropylene skeleton or a polyoxytetramethylene skeleton can be used. As the polyester polyol, a diol having a polycaprolactone skeleton can be used.

Next, the moisture-curable resin (A) comprising a resin composition containing an epoxy resin is a resin composition comprising an epoxy resin and a compound which reacts with moisture to produce an amine. In the above, the epoxy resin is cured by the reaction between an amine produced by a reaction with moisture and the epoxy resin.

As such an epoxy resin, those having two or more epoxy groups in one molecule are preferable. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin,
Bisphenol B type epoxy resin, novolak type epoxy resin, epoxy resin having a naphthalene skeleton, epoxy resin having a fluorene skeleton, epoxy resin made from a copolymer of a phenol compound and dicyclopentadiene, diglycidyl resorcinol, tetrakis (glycidyloxy Glycidyl ether type epoxy resin such as phenyl) ethane, tris (glycidyloxyphenyl) methane, tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine, tetraglycidylbis (aminomethyl) cyclohexane Glycidylamine type epoxy resin, glycidyl such as diglycidyl phthalate, diglycidyl hexahydrophthalate Ester type epoxy resins, and the like which combines a plurality of the epoxy resin can be used.

As the compound which reacts with water to produce an amine, an imine compound, an enamine compound, a silamine compound and the like can be used. The imine compound is a compound obtained by a condensation reaction between a primary amine and a carbonyl compound, and is decomposed into a primary amine and a carbonyl compound when reacted with water. As such a carbonyl compound, for example, acetone, methyl ethyl ketone, cyclohexanone, trimethylacetaldehyde and the like are preferably used. Next, enamine compounds
A compound obtained by a condensation reaction between a secondary amine and a carbonyl compound having a hydrogen atom at the α-position. The compound is decomposed into a secondary amine and a carbonyl compound when reacted with moisture. As such a carbonyl compound, acetone and cyclohexanone are preferably used.

The silamine compound is a compound having a silicon-nitrogen bond obtained by reacting a primary amine or a secondary amine with a silylating agent.
Decomposes into amine and silane compounds. As such a silylating agent, chlorotrimethylsilane and hexamethyldisilazane are preferably used.

The amine functioning as a curing agent for the epoxy resin is preferably a polyamine capable of exhibiting a curing activity at room temperature. Examples of the amine include ethylenediamine, propylenediamine, trimethylenediamine, pentamethylenediamine, and the like.
Diaminocyclohexane, isophoronediamine, mensendiamine, norbornanebis (dimethylamine),
p, p'-methylenebis (cyclohexylamine), m
-Xylylenediamine, p-xylylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like can be preferably used.

The curing accelerator referred to in the present invention is a compound or a compound capable of increasing the curing reaction rate of a moisture-curable resin by blending it with the moisture-curable resin (A) as compared with the case of using only the moisture-curable resin. Means a combination of As such a curing accelerator, the following compounds are used.

As the curing accelerator for the moisture-curable resin (A) of the present invention, a metal compound, a basic compound, an acidic compound, a latent curing accelerator and the like are used.

As such a metal compound, for example, a compound containing a metal element selected from tin, titanium, lead, zinc, iron, aluminum, zirconium and cobalt is used. Such a metal compound is used as a compound having a hydrolyzable silyl group, a compound having an isocyanate group, or a curing accelerator for a resin composition comprising an epoxy resin and a silamine compound. Among these, compounds containing titanium and tin are preferable because of their high curing speed and excellent curability at low temperatures. For example, tetrabutoxytitanium, alkoxytitaniums such as tetrapropoxytitanium, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, dibutyltin diacetate,
Organic tin compounds such as dibutyltin dioctanoate, dibutyltin distearate, dioctyltin oxide, dibutyltin oxide, dibutyltin β-mercaptopropionate polymer, dibutyltin bis (2-ethylhexanoate), tin octoate, tin naphthenate Tin carboxylate salts and the like are preferably used. As other metal compounds, lead naphthenate, phenylmercury propionate and the like can be used.

Next, as the basic compound, amines,
Particularly, a tertiary amine is preferably used. As the tertiary amine, aliphatic tertiary amines and imidazoles are preferably used. Such a basic compound is a compound having a hydrolyzable silyl group, a compound having an isocyanate group,
It is used as a curing accelerator for a resin composition comprising an epoxy resin and a silamine compound.

Examples of the acidic compound include protic acids such as hydrochloric acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, carboxylic acid, sulfonic acid and sulfuric acid monoester, and salts of these with weak bases, Lewis acids, such as boron fluoride, and complexes thereof can be used. Such an acidic compound is used as a compound having a hydrolyzable silyl group or as a curing accelerator for a resin composition comprising an epoxy resin and an imine compound or an enamine compound.

As the above-mentioned latent curing accelerator, any latent curing accelerator of the moisture-curable resin (A) can be used. For example, latent curing activated by heat can be used. The accelerator used is a solid substance that is hardly soluble in moisture-curable resin, a microencapsulated curing accelerator, an inclusion compound that uses the curing accelerator as a guest compound, and a precursor that generates a curing accelerator by a thermal reaction. can do.

In the case of a solid substance that is hardly soluble in a moisture-curable resin, it is activated by dissolving it in a moisture-curable resin by heat treatment. Even a curing accelerator that is easily dissolved in a liquid or moisture-curable resin by itself can be made into a hardly soluble solid by forming a solid solution with a polymer compound having a sufficiently high glass transition temperature. Such a solid solution is activated by elution of the curing accelerator at a temperature exceeding the glass transition temperature of the solid solution. The degree of poor solubility required for the solid substance depends on the process to be used, but it is preferable that the solid substance has sufficient solubility at least at room temperature.
Specifically, it is preferable that 90 parts by weight or more of a solid curing accelerator remain after mixing 1 part of a solid curing accelerator with 100 parts of the moisture-curable resin and leaving the mixture at 20 ° C. for 6 hours.
More preferably, 9% or more remains.

As the microencapsulated hardening accelerator, there can be used particles in which the surface of the hardening accelerator is coated with a wall material such as a thermoplastic resin, a thermosetting resin, or wax. In the case of this microencapsulated hardening accelerator, the heat treatment destroys the wall material of the capsule, and the hardening accelerator inside is activated by being released outside the capsule.

The inclusion compound has a tunnel-like or layer-like network structure (inclusion lattice) formed by a series of atoms or molecules.
Means an intermolecular compound in which another molecule (guest molecule) is confined in the void, and in the case of an inclusion compound in which the curing accelerator is a guest molecule, the curing accelerator which is a guest molecule by heating Is activated by being released. As such an inclusion lattice, clay minerals such as smectite and zeolite are preferably used.

Examples of the hardly soluble solid curing accelerator include, for example, dibutyltin oxide, dioctyltin oxide, dibutyltin maleate polymer, dioctyltin maleate polymer, dibutyltin dichloride,
Dioctyltin dichloride, dibutyltin distearate, dibutyltin dioctoate, dibutyltin β-
Solid organic tin compounds such as mercaptopropionate polymer, dibutyltin bis (2-ethylhexanoate), tin stearate, and “Fujicure” FXE-
1000, FXR-1030 (Fuji Kasei Kogyo Co., Ltd.)
And "Cureduct" ST-0501 (manufactured by Shikoku Chemical Industry Co., Ltd.).

Examples of the microencapsulated curing accelerator include, for example, "NOVACURE" HX-372
1, HX-3722, HX-3741, HX-374
2, HX-3748, HX-3088, HX-3921
HP, HX-3941HP, HX-3613 (manufactured by Asahi Kasei Corporation), "Amicure" PN-23, MY-24
(Ajinomoto Co., Inc.), and a microencapsulated amine compound, and a microencapsulated tin compound disclosed in JP-A-3-186342.
For example, a microencapsulated boron trifluoride complex described in JP-A-223805 can be used.

As a precursor for producing a curing accelerator by the thermal reaction, for example, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts can be used. These are all precursors that generate a protonic acid.

As the latent curing accelerator which can be activated by the light or the electron beam, a precursor which reacts with the energy of the light or the electron beam to produce a curing accelerator is used. In addition, as a precursor for generating an acidic compound, an aryldiazonium salt, a diaryliodonium salt, a triarylsulfonium salt, an aromatic sulfonic acid ester, a carboxylic acid or a nitrobenzyl ester of sulfonic acid, or the like can be used. Further, a cobalt amine complex which forms a basic compound, nitrobenzyl carbamic acid, and the like can also be used.

As a latent curing accelerator which can be activated by mechanical stimulation, a microencapsulated curing accelerator can be used. In this case, the wall material is destroyed by the mechanical stimulation and the internal curing accelerator is released to be activated.

These latent curing accelerators may be used alone or in combination of two or more.

The amount of the latent curing accelerator is preferably 0.01 to 2 parts by weight per 100 parts by weight of the moisture-curable resin.
0 parts by weight, more preferably 0.1 to 10 parts by weight. If the amount is too small, the curing speed will be slow, while
If the amount is too large, the physical properties of the cured product may be reduced.

The resin composition used for the product made of the moisture-curable resin produced by the production method of the present invention may contain various components in addition to the moisture-curable resin and its latent curing accelerator. As such a component, for example, a dehydrating agent or a filler can be blended. By adding such a dehydrating agent, not only can a moisture-cured product be manufactured more stably, but also the storage stability of the moisture-cured product can be improved.

Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and diphenyldimethoxysilane; Isocyanate compounds such as toluenesulfonyl isocyanate, orthoformates such as methyl orthoformate and ethyl orthoformate, and molecular sieves are preferably used. The amount of the dehydrating agent is preferably 0.1 to 100 parts by weight of the moisture-curable resin.
05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

As the filler, organic or inorganic particles or short fibers are used. As organic particles, thermosetting resins, thermoplastic resins, pigments, and the like,
As the inorganic particles, metal, silica, alumina, titanium oxide, zirconia, talc, clay mineral, mica, glass, ferrite, carbon and the like are used. As organic fiber,
Fibers such as polyamide, polyester, and polyimide are used, and glass fibers, carbon fibers, metal fibers, and the like are used as the inorganic fibers. The purpose of compounding these fillers is to color, adjust specific gravity, impart thixotropic properties to uncured resin,
It is to exhibit various effects such as improvement of the elastic modulus and toughness of the cured product, and imparting conductivity, magnetism and vibration damping property to the cured product. As other components that can be blended, for example, dyes, fragrances, brighteners, plasticizers, ultraviolet absorbers, antioxidants, flame retardants, antistatic agents, surfactants, and the like can be blended.

The product comprising the moisture-curable resin (A) produced by the method of the present invention can be put to practical use in several forms of use. For example, a liquid or paste-like composition composed of a moisture-curable resin and a latent curing accelerator can be used to make a bottle, can, case, tube, tank, cartridge, bag, or the like made of a non-permeable material such as metal, glass, or plastic. It can be put to practical use in a form of use sealed in a highly airtight container.

Next, a composition comprising a moisture-curable resin and a latent curing accelerator is applied in the form of a film on a sheet-like substrate such as paper, plastic film, metal foil, etc. To form a cut sheet or a roll, which can be put to practical use in a sealed form in a highly sealed container.

Further, a prepreg formed into a sheet, tape, string, or rope by impregnating the reinforcing fiber with a composition comprising a moisture-curable resin and a latent curing accelerator is used to form a highly airtight container. It is practically used in a form enclosed in a box. As such reinforcing fibers, organic fibers made of cellulose, polyester, polyamide (nylon or aramid) or the like, and inorganic fibers such as carbon fibers, glass fibers, and boron fibers are used. As the form of the reinforcing fiber, a sheet, a woven fabric, a nonwoven fabric, a mat, a knit, a strand, a yarn, a roving, a braid, and the like arranged in one direction are used.

Examples of the use of the product comprising the moisture-curable resin (A) include fillers, adhesives, and adhesives in the fields of civil engineering / architecture, electric / electronics, automobiles, ships, aircraft, sporting goods, arts and crafts, and the like. It can be preferably used for agents, sealing materials, primers, lining materials, coating materials, fixing materials, structural members, reinforcing agents, molding materials, insulating materials and the like.

As more specific examples, sealing materials used to fill joints around panels, tiles and curtain walls, filling gaps between sashes and glass, filling gaps between automobile bodies and glass, anticorrosive paints made of metal materials, In addition, paints used for hydrophilic porous materials such as wood, concrete, stone, etc., lining agents used inside tanks, pipelines, chimneys, etc., adhesives used for wood, concrete, stone, etc. Adhesives and sealing materials used for sealing and fixing electronic components, fixed bandages for medical use (gibbs), injection materials used for repairing cracks in concrete structures, and repair / reinforcement by sticking or wrapping around concrete structures Can be effectively used for various applications such as prepregs.

[0062]

The present invention will be described in detail in the following examples.
The present invention is not limited only to the following. In the examples, all parts indicate parts by weight. Example 1 Bisphenol A type epoxy resin ("Epicoat" 82
8, Yuka Shell Epoxy Co., Ltd.) 100 parts and γ-
Anilinopropyltrimethoxysilane (KBM573,
135 parts (Shin-Etsu Chemical Co., Ltd.) were placed in a flask and reacted at 150 ° C. for 5 hours while stirring under a nitrogen stream.

To 100 parts of the reaction product, 5 parts of a hardly soluble solid curing accelerator (dibutyltin oxide, manufactured by Wako Pure Chemical Industries, Ltd.) were used, and diphenyldimethoxysilane (AY43) was used as a reactive diluent for adjusting viscosity. -547, Dow Corning Toray Silicone Co., Ltd.) were mixed to obtain a moisture-curable resin composition.

The moisture-curable resin composition was applied on release paper using a reverse roll coater, and the resin
A resin film of g / m ² was produced. The glass transition temperature of the moisture-curable resin composition immediately after forming into a resin film was measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (TC10A type, manufactured by METTLER CORPORATION) and found to be −9 ° C. This resin film is heated at a temperature of 25 ° C. and a humidity of 50% for 6 hours.
After standing for a period of time, the glass transition temperature of the moisture-curable resin composition was measured in the same manner. The glass transition temperature was -7 ° C. Further, when the moisture of the moisture-curable resin composition was measured using a trace moisture analyzer (Model CA-02, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), 5 minutes after forming the resin film,
000 ppm, and no change in water content was observed thereafter. Further, this resin film was coated with a carbon fiber woven fabric “Treca Cloth” UT70-30 (woven fabric weight: 300 g /
m ² , manufactured by Toray Industries, Inc.), using a hot roll at 120 ° C. (heating time 30 seconds), 0.5 kg / cm
^The prepreg was prepared by impregnating with ² and simultaneously heating and dissolving the hardly hard solid hardening accelerator. Immediately thereafter, the prepreg was sealed together with nitrogen in an aluminum-deposited polyethylene bag. The above steps were all performed in an atmosphere at a temperature of 25 ° C. and a humidity of 50%.

When the amount of water contained in the prepreg after the sealed storage and the glass transition temperature of the moisture-curable resin composition were evaluated, no water was detected after 6 hours, and the glass transition temperature was 10 ° C. No change in glass transition temperature was observed. Twelve hours after the sealed storage, the prepreg was taken out and allowed to stand for one week in an atmosphere at a temperature of 25 ° C. and a humidity of 50% to obtain a carbon fiber reinforced resin. The glass transition temperature of this carbon fiber reinforced resin was 48 ° C.

COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was carried out except that the hardly-soluble solid hardening accelerator was replaced by a hardening accelerator liquid at room temperature (dibutyltin dilaurate, manufactured by Wako Pure Chemical Industries, Ltd.). To obtain a prepreg, the glass transition temperature of the resin composition after leaving the resin film for 6 hours after production was 2
It was 0 ° C., the resin could not be impregnated into the carbon fiber fabric, and no prepreg could be produced.

Example 2 A polyether having a hydrolyzable silyl group at both terminals was added to 100 parts of the reaction product of the bisphenol A type epoxy resin prepared in Example 1 and γ-anilinopropyltrimethoxysilane ( 50 parts of "Syril" SAT200, manufactured by Kanegafuchi Chemical Industry Co., Ltd., 5 parts of hardly soluble solid hardening accelerator (dioctyltin maleate polymer, manufactured by Wako Pure Chemical Industries, Ltd.), reaction for viscosity adjustment 5 parts of diphenyldimethoxysilane (AY43-047, Dow Corning Toray Silicone Co., Ltd.) was mixed as a water-soluble diluent to obtain a moisture-curable resin composition.

This moisture-curable resin composition was applied on release paper using a reverse roll coater, and the resin weight was 120 g.
/ M2 resin film. A polyester nonwoven fabric (having a basis weight of 30 g / m ² ) is sandwiched between the resin film and release paper, and is heated at 90 ° C. (heating time 30 seconds) using a hot roll.
The film was impregnated with 0.5 kg / cm ² , and at the same time, a hard curing agent which was hardly soluble was heated and dissolved to prepare a film adhesive. Immediately after this, the film-like adhesive was sealed together with nitrogen in an aluminum-evaporated polypropylene bag. The above steps were all performed in an atmosphere at a temperature of 25 ° C. and a humidity of 50%.

The tensile shear strength of the obtained film adhesive was evaluated according to JIS K6850. After taking out the film adhesive from the sealed container, peeling off the release paper on one side and leaving it in an atmosphere at a temperature of 25 ° C. and a humidity of 50% for 15 minutes, using this, an aluminum plate A-1050P of JIS H4000 (100 mm × 25 mm × 2 mm) and left for one month in an atmosphere of a temperature of 25 ° C. and a humidity of 50% to obtain a test piece. When measured at a tensile speed of 50 mm / min, the tensile shear strength was 10.2 MPa.

COMPARATIVE EXAMPLE 2 The same operation as in Example 2 was carried out except that the hardly-soluble solid hardening accelerator was replaced with a hardening accelerator liquid at room temperature (dibutyltin dilaurate, manufactured by Wako Pure Chemical Industries, Ltd.). An attempt was made to obtain a film adhesive, but the resin composition gelled immediately after forming the resin film, and the subsequent steps could not be performed.

Example 3 Polyether having a hydrolyzable silyl group at both terminals (“Silyl” SAT200, manufactured by Kaneka Chemical Co., Ltd.)
100 parts, calcium carbonate 120 parts, titanium oxide 30
, 50 parts of dioctyl phthalate, and 5 parts of a microcapsule-type latent curing agent (“NOVACURE” HX-3721, manufactured by Asahi Kasei Kogyo Co., Ltd.), kneaded using a three-roll mill, and then mixed with a plastic tube. And sealed. The above steps were performed in an atmosphere at a temperature of 25 ° C. and a humidity of 50%. The tube was placed in an oven and heated at 80 ° C. for 60 minutes to activate the microcapsule-type latent curing agent.

Using the moisture-curable resin composition squeezed out of the tube, an H-shaped test piece was prepared according to JIS A5758. Pre-curing was performed at 20 ° C. and 50% humidity for 14 days, and post-curing was performed at 30 ° C. and 50% humidity for 14 days. As a result of performing a tensile test at a tensile speed of 50 mm / min using this test piece, a 50% tensile stress of 0.25 MPa and a strength at break of 0.
The elongation at break was 64 MPa and the elongation at break was 610%.

Comparative Example 3 The same operation was carried out in the same manner as in Example 3 except that a microcapsule-type latent curing agent was replaced with a curing accelerator liquid at room temperature (dibutyltin dilaurate, manufactured by Wako Pure Chemical Industries, Ltd.). Although it was attempted to obtain a moisture-cured resin composition in a tube, the resin composition gelled during kneading using three rolls, and the subsequent steps could not be performed.

[0074]

By using the present invention, it becomes unnecessary to shut off moisture and control low humidity in the manufacturing process, which was indispensable in the past when manufacturing a product made of a moisture-curable resin, thereby simplifying the manufacturing process. Process management becomes easy. For this reason, it is possible to easily and inexpensively produce a product made of a moisture-curable resin having a desired form, which has good storage stability and can be quickly cured when used.

Claims (19)

[Claims] 1. A step of mixing a moisture-curable resin (A) with a latent curing accelerator (B) of the resin (A) (Step 1), and a step of activating the latent curing accelerator (B). (Step 2) A method for producing a product made of a moisture-curable resin, comprising three steps of (step 3) a step of substantially blocking moisture from the composition containing the moisture-curable resin (A). 2. The method for producing a product made of a moisture-curable resin according to claim 1, wherein the method for producing the product is performed in the order of step 1, step 3, and step 2. 3. The moisture-curable resin according to claim 1, wherein the method for producing the product is performed in the order of step 1, step 2, and step 3, and step 3 is immediately after step 2. A method of manufacturing a product comprising: 4. The method for producing a product comprising a moisture-curable resin according to claim 1, wherein said step 2 is a heat treatment. 5. The method according to claim 4, wherein the heat treatment temperature is in the range of 40 to 180 ° C. 6. The method for producing a product made of a moisture-curable resin according to claim 1, wherein said step 2 is a process of irradiating light. 7. The method according to claim 6, wherein the light has a wavelength of 200 to 800 nm. 8. The method for producing a product made of a moisture-curable resin according to claim 1, wherein the step 2 is a process of irradiating an electron beam. 9. The moisture-curable resin according to claim 1, wherein the moisture-curable resin (A) contains a compound having one or more hydrolyzable silyl groups represented by the following general formula (1) in one molecule. A method of manufacturing a product. X _n -Si (R ₁ ) _3-n- (1) (in the formula, X is a hydrolyzable group, n is an integer of 1 to 3, and R ₁ is an alkyl group.) 10. The hydrolyzable group X in the hydrolyzable silyl group is selected from an alkoxy group, an acyloxy group, a ketoximate group, an alkyleneaminooxy group, an acylamino group, an aminooxy group and an alkenyloxy group. A method for producing a product comprising the moisture-curable resin according to claim 9. 11. The method according to claim 1, wherein the moisture-curable resin (A) contains a compound having two or more isocyanate groups in one molecule. 12. The method according to claim 1, wherein the latent curing accelerator (B) is a solid substance that is hardly soluble in the moisture-curable resin (A). 13. The method according to claim 1, wherein said latent curing accelerator (B) is microencapsulated. 14. The method according to claim 1, wherein the latent curing accelerator (B) is an inclusion compound. 15. The method for producing a product comprising a moisture-curable resin according to claim 14, wherein said clathrate compound comprises smectite or zeolite. 16. The latent curing accelerator (B) comprises tin,
The method for producing a product comprising a moisture-curable resin according to any one of claims 1 to 12, which is a compound containing at least one element selected from titanium, lead, zinc, iron, aluminum, zirconium, and cobalt. 17. The method for producing a product comprising a moisture-curable resin according to claim 1, wherein the latent curing accelerator (B) comprises an acidic compound. 18. The method for producing a product comprising a moisture-curable resin according to claim 1, wherein the latent curing accelerator (B) comprises a basic compound. 19. The method for producing a product comprising a moisture-curable resin according to claim 18, wherein said basic compound is a nitrogen-containing organic compound.