JPH0336015A - Method for manufacturing and processing reactive hot melt type composition and preservation method thereof - Google Patents

Abstract

PURPOSE:To improve the handleability and preservation stability of product and, in addition, make the application of general-purpose apparatus possible at the application of the product by a method wherein reactive hot melt type composition is covered by resin having gas barrier properties through a composite extrusion die as the processing method of the form of the moisture-curing reactive hot melt type composition. CONSTITUTION:A kneader-luder type discharger or twin-screw kneader discharger, which aims the manufacturing and discharging of reactive hot melt type composition, and a mono-screw or twin-screw extruder, which aims the extrusion of resin having steam barrier properties, are combined through a composite extrusion die. In addition, the die has a structure which enables the surface of the hot melt type composition to cover with the resin having steam barrier properties by the thickness of 5 - 200mum. The melt type composition is continuously coated with the resin having steam barrier properties by the thickness of 5 - 200mum and, after that, processed in the form of beads, strands or pellets.

Description

DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field The present invention relates to a method for manufacturing and storing a four-cure reactive hot-melt composition.

[Prior art and its problems] Conventionally, moisture-curable reactive hot-melt adhesive compositions have been disclosed in JP-A No. 49-25033, JP-A No. 51-90342, and JP-A No. 51-90342. "58-175
No. 14”, JP-A-Sho-r No. 58-67772”, JP-A-Sho-r
No. 58-147473'', Japanese Patent Publication No. 59-68:1
I85'', Japanese Patent Publication No. 57-15827fi'', Japanese Patent Publication No. 60-28476'', Japanese Patent Publication No. 47-518'', Japanese Patent Publication No. 4! No. 1-98445”, Japanese Patent Application Publication No. 1983-1951
-30898 J, etc., ethylene-vinyl acetate type, polyolefin; f- (represented by low density polyethylene type and atactic polypropylene type), block polymer type (SIS).

Various moisture-curable reactive hot-melt compositions are known, which consist of a thermoplastic rubber component mainly composed of SBS, 5EBS, butyl rubber, polyester, or polyamide, and an isocyanate prepolymer. , also Tokuko Showa No. 59-52677'', to Tokuko Showa 60 33
As seen in No. 52 J, etc., hydrolyzable active silyl groups are grafted onto ethylene-vinyl acetate resin or polyethylene resin using a radical initiator such as A oxidation catalyst or azo catalyst to make it the main component. Reactive hot melt compositions are also known. However, there are very few disclosures of techniques for safely manufacturing and processing the above-mentioned reactive ret-melt and its storage method, which is currently an obstacle to the development of the composition.

In particular, non-reactive hot-melt adhesive compositions are widely used in industries such as bookbinding, packaging, textiles, furniture, woodworking, light electrical appliances, and transportation, and are becoming increasingly important in terms of ease of handling and high productivity. With regard to reactive hot-melt adhesives, there is currently a strong demand for product forms that are as simple and highly productive as conventional hot-melt adhesives. The main problem is that moisture-curable reactive hot-melt compositions deteriorate over time when exposed to high humidity indoors, and cannot be remelted. A preservation method is required.

In the field of product assembly, there is a strong demand for the use of heat-resistant, moisture-curable, reactive hot-melt adhesive compositions that take advantage of the initial adhesive strength of hot-melts, are easy to handle, and can be produced at high production rates. It is desired to develop a method for processing and preserving a shape that has good flexibility and lineability.

Until now, no technology has been found regarding a manufacturing method and a storage method that meet the above-mentioned industry demands. That is, −
For example, a manufacturing method and a storage method in which drums are directly filled and sealed have been proposed and have been adopted in some departments, but they require special equipment, are complicated, and are extremely inefficient.

That is, in the field of product assembly, line stoppages when switching drums are often a problem, resulting in low continuous productivity.

[Problems to be Solved by the Invention] An object of the present invention is to process a moisture-curable reactive hot-melt composition into a product form that can be used with a known general-purpose applicator, as well as to process it in a form that is easy to handle. The object of the present invention is to provide a manufacturing processing method and a storage method that are simple and can be stored for a long period of time.

[Means for Solving the Problems] The present invention provides a kneader-ruder type discharge machine or a twin-screw kneading discharge machine for the purpose of producing and discharging a reactive hot melt type composition, and a resin having water vapor gas barrier properties. A single-screw extruder or twin-screw extruder for the purpose of extrusion processing is
Using manufacturing equipment coupled through a composite extrusion die,
In addition, by forming a die structure that allows the surface of the hot melt composition to be coated with a resin having water vapor gas barrier properties to a thickness of 5 to 200 microns, the hot melt composition can be coated with a resin having water vapor gas barrier properties. 5-20
This invention relates to a method for manufacturing and processing a moisture-curable reactive hot-melt composition, which is characterized by continuous coating to a thickness of 0 microns and processing into bead, strand, or pellet shapes. Preferably, a resin selected from polyethylene resin, polypropylene resin, polyvinylidene chloride resin, paraffin wax resin, and natural wax resin is used as the water vapor gas barrier resin.

Furthermore, the present invention provides a method for preserving products after manufacturing and processing.
The surface of the reactive hot-melt composition is coated with a gas barrier resin selected from polyethylene resin, polypropylene resin, polyvinylidene chloride resin, paraffin Fuchs' vote resin, and natural wax resin to a thickness of 5 to 200 microns. The product is packed in a polyethylene bag and stored in a paper/cardboard box, and the bead-shaped, strand-shaped, or pellet-shaped product obtained by the above-mentioned coating is stored in a polypropylene box with a capacity of 1 to 50 liters or a cardboard box. Either replace the product with nitrogen and store it in a sealed container, or insert the above product into a steel plate open drum with a capacity of 1 liter to 200 liters with a 1A contact or polyethylene bag inside, replace it with nitrogen, and store it in a sealed container. The present invention relates to a method for preserving a moisture-curable reactive hot-melt composition.

Further, in the present invention, the main components are a urethane prepolymer formed by reacting a mixed polyol consisting of a hydrocarbon polyol containing heavy terminal hydroxyl, a polyether polyol, and a diisocyanate compound, and a thermoplastic rubber component. The reactive hot-melt composition or the reactive hot-melt composition has the general formula -3i -(Y) 3-n
(However, Y represents a hydroxy group, an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, an allylamino group, an alkylamino group, and an oxime group, respectively, and n represents an integer of 0.1 or 2.) It is preferable to use a reactive hot-melt composition containing a silyl-modified prepolymer resin into which active silyl groups have been introduced.

The configuration of the present invention will be explained in detail below.

Desired reactive hot-melt composition: The reactive hot-melt composition of the present invention is composed of a thermoplastic rubber, a tackifier, a wax, a plasticizer, an antioxidant, an ultraviolet absorber, or the like. A resin composition consisting of a thermoplastic rubber component and a urethane prepolymer consisting of two or more components, or a hydrolyzable resin composition instead of or in combination with a thermoplastic rubber component or a urethane prepolymer. Typical examples include compositions containing as a main component the silyl group-modified prebonomer resin into which active silyl groups exhibiting properties are introduced, and may be conventionally known reactive hot-melt compositions. , there are no particular restrictions. Preferred reactive hot-melt compositions include a urethane prepolymer formed by reacting a saturated hydrocarbon polyol containing hydroxyl groups at both ends, a mixed polyol such as a polyether polyol, and a diisocyanate compound, and a thermoplastic Compositions containing rubber components are promising as structural adhesives for product assemblies, and are cited as preferred examples.

More preferable reactive hot-melt compositions include compositions containing as a main component a silyl group-modified prepolymer resin into which the active silyl groups have been introduced, particularly for molding glass, metals, and polyester resins for bond adhesion resistance. It is very promising as a structural circumferential R method for assembling structures such as objects, etc., and is cited as a preferred example.

Here, thermoplastic rubber refers to ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA), ethylene-ethyl acrylate copolymer 1Mm <hereinafter referred to as EEA>, ethylene-vinyl acetate copolymer resin (hereinafter referred to as EEA),
Methyl acrylate copolymer resin (hereinafter referred to as EMA),
Styrene-isoprene-styrene block copolymer resin (
(hereinafter referred to as SIS), styrene-butadiene-styrene block copolymer resin (hereinafter referred to as SBS), styrene-butadiene-styrene block copolymer resin (hereinafter referred to as SBS),
Ethylene-butylene-styrene block copolymer resin (hereinafter referred to as 5EBS), ethylene-propylene copolymer resin (hereinafter referred to as EPR), butyl rubber, isoprene rubber,
A thermoplastic resin consisting of one or more types represented by isobutylene rubber, acrylic rubber, urethane rubber, nitrile rubber, etc. Among them, butyl rubber, 515.
SBS, 5E8S, EE^.

A polymer consisting of one or more selected from EV^ and EPR is preferred. Special EEA, EVA, SIS, S
It is cited as a preferred example because of its high moisture permeability.

Tackifiers include (hydrogenated) rosin, (hydrogenated) rosin ester, (hydrogenated) rosin ester conductor, terpene resin, terpene-phenolic resin, aliphatic type, aromatic type, copolymer type, alicyclic type. Typical examples include petroleum resins such as petroleum resins and hydrogenated petroleum resins, coumaron-indene resins, xylene resins, and ketone resins, and these may be used alone or in blends.

Further, as the tackifier, the following are preferred examples in consideration of affinity with the urethane prepolymer, reactivity, and hue, and it is preferable to use them alone or in a blend.

That is, the rosin or rosin esters include rosin hydrogenated rosin, (hydrogenated) rosin glycerin ester, and (hydrogenated) rosin pentaerythritol ester, and the terpene-phenol network includes resins with a softening point of less than 130°C. Stone 7111 resins include C5 fractions such as pentenes, isoprene, piperine, and cyclopentadiene produced by thermal decomposition of stone extracted naphtha, vinyltoluene, α- or β-methylstyrene, also produced from stone extracted naphtha fraction M, , dicyclopentadiene, indene, etc., and a hydrogenated petroleum resin mainly composed of a copolymer composition of the above-mentioned C3-C9 fraction and having a softening point of less than 125° C. is preferable.

The amount of tackifier added is generally 30 to 800 parts by weight, preferably 50 to 300 parts by weight, per 100 parts by weight of the thermoplastic rubber component. In this case, if 3 or B is less than 1 part, the hot-melt composition will have poor wetting properties to the adherend, adhesion, low viscosity during melting, etc.;
If the amount is more than 0 parts by weight, the rubber will lack elasticity and become brittle.

Examples of the wax include paraffin wax, microcrystalline wax, Fischer tropic wax, polymerized wax, low molecular weight polyethylene wax, low molecular weight polypropylene wax, beeswax, spermaceti wax,
Typical examples include natural waxes such as carnauba wax, wood wax, montan wax, and osikerite, and modified waxes.

The amount of wax added is 100% of the thermoplastic rubber component.
Less than 500 parts by weight, preferably 10 to 1 part by weight
It is used in an amount of 100 parts by weight.

If the amount is more than SOO parts by weight, the rubber elasticity will be poor and the rubber will become brittle.

Examples of plasticizers include liquid polyisobutyne, liquid polybutene, liquid (hydrogenated) polyisoprene, liquid (hydrogenated)
Typical examples include polybutadiene, paraffinic oil, naphthenic oil, epoxy plasticizer, phosphoric acid esters, phthalic acid esters, aliphatic dibasic acid esters, glycol esters, etc., and they may be used alone or in a blend. Liquid polyisobutyne, liquid polybutene, liquid (hydrogenated)
Hydrocarbon plasticizers such as polyisoprene, liquid (hydrogenated) polybutadiene, paraffin oil, and naphthenic oil are more preferred in terms of affinity.

The amount of plasticizer added is less than SOO parts by weight, preferably 10 to 10 parts by weight, based on ioo parts by weight of the thermoplastic rubber component.
Use within the range of 0 parts by weight.

If the amount exceeds 500 parts by weight, problems arise in terms of initial adhesive strength and cohesive strength in the melt state.

The antioxidant (antiaging agent) is preferably a hindered phenol, and is used in an amount of less than 5 parts by weight, preferably from 0.2 to 1 part by weight, based on 10 parts by weight of the thermoplastic rubber component.

As the ultraviolet absorber (ultraviolet stabilizer), hindered amines are preferred, and are used in an amount of less than 5 parts by weight, preferably from 0.2 to 1 part by weight, based on 100 parts by weight of the thermoplastic rubber component.

As the filler, an inorganic or organic filler having the function and effect as a known filling reinforcing agent may be used, such as calcium carbonate, barium sulfate, talc, clay, titanium oxide, silica, colloidal silica, carbon black, and glass powder. Alternatively, there are glass fibers, urea-melamine resin powder, acrylic resin powder, phenol reticulum powder, etc., which may be used alone or in a blend.

As the urethane prepolymer, it can be used as long as it has high compatibility with the above-mentioned thermoplastic rubber component and the isocyanate content is preferably in the range of 2.0 to 15% by weight, and it has good weather resistance, heat aging resistance, etc. Considering the reliability of saturated hydrocarbon polyols containing hydroxyl groups at both ends, polyether polyols, polyester polyols,
Examples include urethane prepolymers made by reacting acrylic polyols and diisocyanate compounds. It is important to select and adjust the composition so as to provide a composition that is highly compatible with the thermoplastic rubber component and has excellent toughness and weather resistance such as non-yellowing.

The saturated hydrocarbon polyol containing hydroxyl groups at both ends includes a completely new diol that has not been known until now, such as an ethylene-propylene copolymer polyol containing hydroxyl groups at both ends with a weight average molecular weight of 5.000 or less; It is preferable to use an ethylene-butylene copolymer polyol containing hydroxyl groups at both ends, a polyisobutylene polyol containing hydroxyl groups at both ends, and the like.

As the diisocyanate compound for obtaining the urethane prepolymer, known diisocyanate compounds may be used, such as 2,4-tolylene diisocyanate, 2,6-1 lylene diisocyanate, diphenylmethane diisocyanate, etc. Typical examples include anato, α, α, α°, α゛-tetramethylxylylene diisocyanate, metaxylylene diisocyanate, and hydrogenated compounds thereof, as well as isophorone diisocyanate, tetramethylene diisocyanate, etc. In addition, diphenylmethane diisocyanate-based and tolylene diisocyanate-based polyisocyanates can also be employed as the diisocyanate compound.

It is common to use one or a mixture of two or more of these.

In addition, when providing a reactive hot-melt composition that particularly requires weather resistance, it is preferable to use hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, and the like.

The urethane prepolymer may be adjusted by adjusting the reaction ratio (NCOloll) between the hydroxyl group equivalent of the polyol and the isocyanate group equivalent of the diisocyanate compound in the range of 1.9 to 3.0. If it is less than 1.9, it is undesirable because a significant thickening phenomenon occurs as the equivalence ratio decreases, or it lacks thermal stability. On the other hand, if it is more than 3.0, a large amount of free isocyanate components will be present. During the application process, significant amounts of free isocyanate vapor are generated, causing environmental pollution and rapid curing reactions.
This is undesirable because it causes more foaming than necessary due to moisture in the air.

However, if the purpose is to obtain the material by foaming, for example, foamed materials are preferable for use in cap seals for bottles, etc., so there is no particular limitation.

Typical examples of polyether polyols include those having a weight average molecular weight of 2,000 or less. Polycarbonate polyols, propylene oxide and/or ethylene oxide adducts of bisphenol A and/or bisphenol F, polytetramethylene ether glycol, propylene oxide and/or ethylene oxide adducts of glycerin, polyoxybutylene glycol, polyoxypropylene glycol,
etc. are representative.

In addition, conventionally known polyether type polyols,
Ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol,
The present invention also encompasses the combined use of general polyols such as sorbitol, monool, and polyols obtained by graft polymerizing styrene and acrylonitrile to polyoxypropylene glycol.

General formula -Si-(Y)3-n (However, Y represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, an allylamino group, an alkylamino group, or an oxime group, respectively, and n is 0.1 or The silyl group-modified prepolymer resin into which active silyl groups are introduced is represented by the following integer 2.

That is, for example, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) is added to the thermoplastic rubber or tackifier using a peroxide catalyst or an azo catalyst.
silane, vinylsilanes such as vinyltriethoxysilane, α-methacryloxymethyltrimethoxysilane,
γ-methacryloxypropyldimethoxymethylsilane,
Acryloylsilanes such as γ-methacryloxypropyltrimethoxylane and γ-methacryloxypropyltriethoxysilane, and mercaptosilanes such as (γ-mercaptopropyl)methyldimethoxysilane and γ-mercaptopropyltrimethoxysilane, or after grafting an unsaturated acid anhydride or unsaturated acid to the thermoplastic rubber or tackifier using a peroxide catalyst or an azo catalyst, e.g. , γ-glycidoxybrobyltrimethoxysilane, γ-glycidoxybrobylmethyldimethoxysilane, γ-glycidoxybrobyltriethoxysilane, γ-glycidoxypropylmethyljethoxysilane,
Glycidylsilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; or N-
Resin obtained by condensing aminosilanes such as β(aminoethyl)-γ-aminopropyltriethoxysilane and γ-aminopropyltriethoxysilane: Acetoxysilane is obtained by reacting an alkoxysilane group with, for example, acetic anhydride by a known method. Using a diperoxide catalyst or an azo catalyst, a chlorosilane group-introduced resin grafted with a nylsilane such as vinyltrichlorosilane is reacted with an alkylamine to form an alkylaminosilane group using a known method such as an alkylamine. Examples include resins obtained by reacting with known oxime compounds and modifying the oxime silanol groups.

Thermal IiT plastic rubbers to which unsaturated acid anhydrides or unsaturated acids have been grafted in advance are already commercially available. Name Clayton FG-
It is available as 1901XJ and can be preferably used.

For example, among the above-mentioned tackifier resins, (water t!A) rosin, rosin ester derivatives, acid-modified polyethylene wax, acid-modified polypropylene wax, etc., glycidylsilanes are reacted with the carboxyl groups to make them active within the molecule. A method of introducing a silyl group to produce a relatively low-molecular silyl group-modified prepolymer resin, or, for example, using the above-mentioned acryloylsilanes or vinylsilanes with other copolymerizable monomers, such as acrylate monomers or styrene monomers. Typical examples include resins obtained by copolymerizing acrylonitrile monomers with ethylene monomers, propylene monomers, and the like.

It is preferable that the silyl group-modified prepolymer resin has at least 0.2 or more active silyl groups introduced into its molecules on average to improve adhesion reliability. The introduction of the above components is highly preferable because the heat-resistant rigidity of the reactive hot-melt composition can be dramatically improved.

In the reactive hot-melt composition containing the silyl group-modified prepolymer resin, the above-mentioned thermoplastic rubber, tackifier wax, plasticizer, and antioxidant are added, as in the urethane prepolymer-containing reactive hot-melt composition. ,
There is no problem when it contains an ultraviolet stabilizer, and there is no problem when it is used in combination with the urethane polymer.

There are no particular restrictions on the content of the silyl group-modified prepolymer resin, but in consideration of the melt viscosity and workability of the composition, it is preferably within a range of approximately 70% by weight or less, preferably within 50% by weight.

However, this does not mean that it cannot be used as a stand-alone system at all.

In general, silyl group-modified prepolymer resin has a silyl group modification in the resin of 5! ] If the amount of E is more than % I, more foaming than necessary may occur during curing.

However, this is not the case when the composition is intended for foaming.

As additives, the following reaction curing accelerators are used in order to improve the reactivity of active isocyanate groups and active silyl groups with moisture. It may be used in an amount ranging from 1 to 5% by coul. Dibutyltin dilaurate and tertiary amine are used alone or in combination as preferred reaction curing accelerators. Particularly preferred are dibutyltin dilaurate and 1,3-dimethylimidazolidinone or 1,3-dimethylimidazolidinone mono-11 as the tertiary amine, since they can simultaneously satisfy the effects and odorlessness.

Furthermore, reactive hot-melt compositions can be colored and cured.
The purpose of this product is to improve thermal stability, adjust the coefficient of thermal expansion and contraction, and alleviate residual stress at the adhesive or coating interface.
It is preferable to add and blend the following fillers within 30% by weight.

Preferred fillers include one or more powders selected from zinc oxide, magnesium oxide, metal, silica (including colloidal silica), calcium carbonate, titanium oxide, talc, alumina, carbon black, etc. A filler made of In particular, the use of powders such as zinc oxide, calcium carbonate, titanium oxide, talc, and carbon black has favorable effects such as significantly improved weather resistance and high thermal stability of the system. If the filler is used in an amount exceeding 3 offi-1 t%, the system exhibits high thixotropy in terms of viscosity, resulting in a decrease in workability. Further, it is not preferable because it has disadvantages such as significantly accelerating wear of the hot melt applicator.

In addition to this, known organic pigments, organic dyes,
Inorganic pigments other than those mentioned above may also be added to the reactive hot melt composition, and conventionally known antioxidants (antiaging agents) such as phosphoric acid esters, ultraviolet absorbers such as benzotriazole, and organic thixosols may be added. There is no problem in using a surface modifier such as a imparting agent, a silane or a titanate coupling agent, etc. in combination as appropriate.

Manufacturing and processing method: The manufacturing and processing method of the present invention is not particularly limited with respect to the manufacturing equipment itself, and basically uses a water vapor gas barrier.
By using a composite extrusion die that can coat the surface of a reactive hot melt composition with a resin having properties of 5 to 200 microns in thickness, moisture-curable reactive hot melt compositions can be coated with water vapor gas barrier properties. 5-20 in resin with
We propose a processing method characterized by continuous coating to a thickness of 0 microns and processing into beads, strands, and pellets.

The manufacturing and processing method of the present invention can be employed after the reactive hot-melt composition is prepared in advance using a separate device or immediately before processing.

There are no particular restrictions on the composite extrusion die structure, but
Preferably, the die temperature at the center of the die is preferably a structure that has a temperature control function that takes into consideration changes in thermal properties of the reactive hot melt composition, and ranges from room temperature to 120°C, preferably from 50°C to 120°C. It is important that the structure is designed to maintain a die center temperature of 80°C.

In addition, it is important to set the die peripheral temperature of the gas barrier resin molding part of the composite extrusion die to an appropriate temperature depending on the type of resin that has gas barrier properties, but there is also a relationship with the reactive hot melt type composition. Taking this into account, it is desirable to have a structure that can be adjusted to a temperature of 180°C or less, preferably at most about 150°C, particularly preferably 120°C or less.

As mentioned above, the die temperature of a resin having gas barrier properties is generally much lower than the optimum melting temperature of the resin, so it is preferable to have a die structure that can minimize the residence time in the die.

When using a die temperature of a resin with gas barrier properties at a high temperature of 150°C or higher, the strands of the reactive hot melt composition should be coated and contacted with the gas barrier resin after passing through the die as much as possible, and composite extrusion It is preferable that the die has a structure that simply functions as a mold for extruding and molding both at the same time.

That is, the composite extrusion die has a nozzle opening at its center that determines the morphology of the reactive hot melt composition;
It has a structure with a slit nozzle opening on the outer periphery that determines the form processing of the resin that has gas barrier properties for coating, and each nozzle part has a separate heating temperature adjustment function that allows processing at the target resin temperature. Things are good.

In the present invention, the following resins can be preferably employed as the resin having gas barrier properties. That is, polyethylene resin, polypropylene resin, polyvinylidene chloride resin,
Examples include paraffin wax resins, natural wax resins, etc., and in particular, low molecular weight high density polyethylene, polypropylene, paraffin wax resins, and natural wax resins alone or in combination with the other resins mentioned above. A mixed resin system is preferred because it has high low-temperature processability and water vapor gas barrier properties.

The coating thickness of the resin that makes the gas barrier property 4 is 5 to 200.
The reason for choosing the micron range is that it is extremely difficult to coat with a diameter of 5 microns or less by coextrusion processing, and the effect of preventing moisture absorption deterioration of the reactive hot melt type composition is small. On the other hand, if the gas barrier resin coating is larger than 200 microns, the storage stabilization effect is not significant, the cost is high, and the resin has reactive hot spots during coating due to heat engraving during molding of the resin that has gas barrier properties. This is because the melt-type composition is thermally degraded more than expected due to preheating of the coated mesh cylinder, which may cause problems such as discoloration, gelation, and thickening of the composition.

In addition to the processing method of coating the reactive hot-melt composition with a resin having gas barrier properties, the present invention also includes a method of preserving the product obtained after processing the reactive hot-melt composition. This is an important handling method, and the preservation method of the present invention will be described below.

Preservation method: The preservation method of the present invention refers to a processed product that is coated with the above-mentioned resin having gas barrier properties to a thickness of 5 to 200 microns so as to completely envelop the surface of the reactive hot-melt composition. This is a method of preserving food without altering its quality for a long period of time, and is explained below.

One of the methods is to process the reactive hot-melt composition into beads, strands, or pellets using the method described above, place it in a thick plastic bag of 100 microns or more, replace it with nitrogen, and then seal it. An example of this method is to package and store the product in a paper/cardboard box.

More preferably, there is a method in which the reactive hot-melt composition obtained by processing the shape by the above-described method is stored in a polypropylene container with a capacity of 1 to 50 liters after purging with nitrogen and then being sealed and packaged. .

Most preferably, the reactive hot-melt composition obtained by the above-mentioned method is placed in a steel oven-type drum container with a capacity of 1 to 50 liters, and then replaced with nitrogen, either directly or through a plastic bag. Preservation methods include airtight packaging.

Any known storage container may be used. That is, in the method for preserving a reactive hot melt composition of the present invention, a reactive hot melt composition coated with a resin having gas barrier properties is mainly used. Only by means of form processing, the obtained reactive hot-melt composition can satisfy long-term storage stability even if a known simple packaging container is used.

Furthermore, the preservation method of the present invention is superior in that it is easy to handle, has a high degree of freedom in repeatedly opening and closing the packaging container, allows the required amount to be taken out at any time, and allows the use of general-purpose applicator equipment. A preservation method that has not been able to be used up to now as a packaging means for moisture-curable reactive hot-melt compositions can be adopted.

Usage method: Regarding the use of the reactive hot-melt composition of the present invention after shape processing, as a result of consideration in view of the product form, the following usage method was found to be the best from the viewpoint of automation suitability and line passability. .

In other words, when using a reactive hot-melt composition obtained by shape processing, the method of use is as follows: When using a reactive hot-melt composition obtained by shape processing, a resin protective film having gas barrier properties can be melted and mixed with the reactive hot-melt composition. It is possible to use a method of melting with an applicator that has a discharge defoaming mechanism. For example, it is possible to use a kneader with a biting roll.
A single or double screw type extrusion mechanism applicator (with different diameters) that can be continuously supplied to the kneading mechanism and heated.
Examples include a method in which defoaming, kneading, and discharging are performed using a so-called kneader-ruder type applicator.

More preferably, the gas-barrier resin h) of the reactive hot-melt composition obtained by shape processing is slitted and removed from the protective film layer before use, and only the reactive hot-melt composition is formed. It is preferable to use it by melting and discharging it with an applicator capable of melting, kneading, and defoaming.

Also, most preferably, the protective barrier film is removed by a slitter installed in front of the biting roll, and the hot melt type composition is continuously supplied and melted by the biting roll to the melting mechanism of the applicator, and the product is heated. It is preferable to use a so-called extrusion mechanism applicator capable of defoaming, kneading, and discharging using a single-screw or twin-screw extruder of different diameters.

[Examples] The present invention will be specifically explained below with reference to Examples, but these descriptions are not intended to limit the present invention in any way. In addition, % and parts described in the working steel mean % by weight and parts by weight, respectively.

In addition, as an apparatus for manufacturing and processing the moisture-curable reactive hot-melt composition described in Table 1 of Example 1, the following apparatus was used.

After adjusting and defoaming the reactive hot melt type composition using a closed type kneader/ruder type kneader with a kneading capacity of 10 liters manufactured by Yotsuyama Seisakusho, the reactive hot melt type composition was prepared by rotating the router in the normal direction. , from the center die opening of the composite extrusion die directly connected to the kneading machine, at a die temperature of 80℃, 20x5a
It was extruded into a strand with a width of +m. On the other hand, as an extruder for resin with gas barrier properties, a model manufactured by Kurimoto Iron Works
Using an inch two-screw continuous kneader, the outer slit nozzle of the composite extrusion die, which is also directly connected to the extruder, is used to simultaneously extrude and pressurize the outer periphery of the die at different processing temperatures. A resin having a gas barrier property is coextruded and then contact coated on a strand of the product, and a resin having a gas barrier property is coated on the surface of the strand of the reactive hot melt type composition.
This was carried out using an apparatus capable of coating to a thickness of 100 μm. However, after coextrusion, the material was blown with cold air, coated with a resin having gas barrier properties, and immediately cooled by placing it on a water-cooled belt cooler to obtain a continuous tape-like strand of 30 cm to 100 m. The ends of the tape were sandwiched using a pressure press heat sealing machine, and the resins with high gas barrier properties were fused together and then cut. The obtained strand-shaped tape was wound up and subjected to the following test.
The results are listed in Table-2.

Example! Ethylene-ethyl acrylate copolymer resin Nimitsui DuPont Polychemical Co., Ltd. product, trade name Evaflex A-7
150 parts of 03, 100 parts of tackifier Nitonex Co., Ltd., trade name Kokoretsu 5320 (hydrogenated dicyclopentadiene petroleum mesh body), and 20 parts of wax Nippon Seiro Co., Ltd. product, paraffin wax HNP-3. and plasticizer Nippon Petrochemical Co., Ltd. product, trade name Shiroishi Polybutene) (5 parts of V-300 was added to the horizontal Ni-Goo, after the official, 160
The thermoplastic rubber component (1>
And so.

In addition, instead of the ethylene-ethyl acrylate copolymer resin, a styrene-isobrene-styrene block copolymer resin produced by Nigel Chemical Co., Ltd., trade name Kaliwarex T
A thermoplastic rubber component (2) was obtained in the same manner except that 150 parts of R-1112 was used.

On the other hand, the reaction of 300 parts of a saturated ethylene-brobylene copolymer polyol containing hydroxyl groups at both ends with a hydroxyl equivalent of 0.90 meq/g and an average molecular weight of 2.500: produced by Idemitsu Petrochemical Co., Ltd., trade name PIP-H Pour into pot, 120
After dehydration treatment under vacuum at °C, the temperature of the system was set to 85 °C, and 55.6 parts of isophorone diisocyanate was added in a nitrogen stream (NC01011 = 2.05) L/L, and the mixture was reacted for 8 hours to form a mixture containing NCO. A urethane prepolymer (A-1) having an amount of 3.3% was obtained. Moreover, instead of the isophorone diisocyanate, a substituted product at the 2.4-position and a substituted product at the 2.6-position are substituted with the 8
N0 was prepared in the same manner except that 43.8 parts of 80/20-tolylene diisocyanate were present in a ratio of 0:20.
A urethane prepolymer (A-2) containing 0% and 3.0% was obtained.

On the other hand, a glycerin propylene oxide adduct type polyol with a hydroxyl equivalent of 4.19 eq/g and an average molecular weight of 700: a product of Mitsui Toatsu Chemical Co., Ltd., trade name MN-70.
After 300 parts of hydrogenated diphenylmethane diisocyanate was charged into a reaction vessel and dehydrated under vacuum at 2120°C, the temperature of the system was raised to 85°C, and 332 parts of hydrogenated diphenylmethane diisocyanate was immersed in a nitrogen stream (NC).
01011=2.00), react for 5 hours, and then
Urethane prepolymer with GO content of 8.5% (B-1)
I got it.

Moreover, instead of the hydrogenated diphenylmethane diisocyanate, a substituted product at the 2.4-position and a substituted product at the 2.6-position were used at a ratio of 80:2
The same procedure was followed except that 229 parts of 80/20-tolylene diisocyanate were present in a ratio of 9.
A 4% urethane prepolymer (B-2) was obtained.

On the other hand, the hydroxyl equivalent of 300 parts of PIP-H is 7.4.
9 meq/g, 300 parts of propylene oxide adduct type polyol of glycerin with an average molecular weight of 400: Mitsui Toatsu Chemical Co., Ltd. product, trade name MN-400 was charged into a reaction vessel.
After dehydration treatment under vacuum at 120°C, the temperature of the system was set to 85°C, and 645 parts of hydrogenated diphenylmethane cysocyanate was introduced in a nitrogen stream (NGO10H = 2.02). A urethane prepolymer (A B-1) having a content of 8.4% was obtained.

Next, 30 parts of thermoplastic rubber component (1), 50 parts of urethane prepolymer (A-1), and 20 parts of urethane prepolymer (B-1) were put into the closed type nider-rugoo whose temperature was controlled at 85°C.
Mixed for 1 hour under a stream of nitrogen, then defoamed under vacuum for 10 minutes, No.

The reactive hot melt composition (a) was prepared and subjected to the manufacturing and processing test described above.

Next, thermoplastic rubber components (1), (2) and urethane prepolymers (^-1>, (8-2), (B-1), (B
-2) and (B-1) were similarly blended in the proportions listed in Table-1.

Reactive hot-melt composition No. listed in Table-1.

(a)-No. (force) was obtained and subjected to the manufacturing and processing test described above.

Table 1 Example 2 Maleic anhydride-modified styrene-ethylene-butylene-styrene block copolymer resin 1000 parts of Nigel Chemical Co., Ltd. product, trade name Kraton FG-1901X, and rosin ester resin as tackifier: Arayo Kagaku Co. product ,
Product name Super Esthetic jLzA-115 (7) 1000
1.0 parts were uniformly mixed and dissolved in a kneader/lugoux of 100 parts each at a kneading melting temperature of 150°C, and 1 part was mixed and dissolved under vacuum.
After partial dehydration, the pressure was reduced to normal pressure, 0.5 parts of 1,3-dimethylimidazolidinone and 75 parts of γ-glycidoxypropyltrimethoxysilane were added in a nitrogen stream, and the mixture was heated for 1 hour to undergo silyl group introduction modification. A prepolymer resin (S-1) was prepared.

Obtained silyl group-introduced modified prepolymer resin (S-1)
was a modified net shell composition having approximately 90% or more of active trimethoxysilyl groups based on the acid value measurement results.

Subsequently, 2250 parts of a dried hydrogenated terpene resin: Clearon P-115 (trade name, manufactured by Yasushi Oil Co., Ltd.), and 3 parts of polypropylene wax having an average molecular weight of 3,500 were added to this system.
Then, 500 parts of Nisseki Polybutene HV-100 (trade name, manufactured by Nippon Petrochemical Co., Ltd.) as a plasticizer were added and uniformly melted. Finally, silyl group-introduced modified prepolymer resin (S
A reactive hot-melt composition (P-1) containing about 40% of -1) was obtained.

The melt viscosity of the reactive hot melt composition (P-1) is 1
Various gas barrier resins shown in Table 3 were tested in the same manner as in Example 1, except that the center die processing temperature was 130 to 150°C. A coated specimen was prepared and subjected to the following storage stability test.

Storage Stability Test - Eight Samples shaped into strands (30 ctn length test piece) were placed in a constant temperature and humidity chamber at 20°C/65% RH for one month, and then taken out to determine the reactive hot melt composition. The change in melt viscosity was measured, and the rate of change between the initial value and the value after the test was determined.

Storage Stability Test-B Each sample shaped into a strand (+00+n length test piece) was placed in an open drum made of round rolled steel plate, and after being purged with nitrogen, the drum was sealed with a metal lid via a rubber gasket.
After being allowed to stand for several months, the composition was taken out, and the change in melt viscosity of the reactive hot melt composition was measured, and the rate of change between the initial value and the value after the test was determined.

Storage Stability Test-C After inserting each strand-shaped sample (30cIII length test piece) into a 200 μ-thick high-density polyethylene bag with a zipper, purge with nitrogen and tighten the zipper. Closed and placed in a constant temperature and humidity chamber at 20°C/65% RH for one month, it was taken out and the change in melt viscosity of the reactive hot melt composition was measured, and the rate of change between the initial value and the value after the test was calculated. I asked for it.

In addition, the results of the storage stability tests 1 to 3 were displayed as follows. In other words, ◎ indicates that the rate of change is within +10%, and E~ indicates that the rate of change is greater than +10%.
+30% or less is O, and the rate of change is +30% or more -E to +10
If the rate of change was within 0%, it was rated △, and if the rate of change was +100% or more, it was rated x.

Table-2 Table-3 Low-density PE: Mitsui Nisseki polymer product name "Mirason J used, extruder processing temperature 170℃, die processing temperature 120℃ High-density PE: Nippon Petrochemical "Stablen" extruder processing temperature 200℃, Die processing temperature: 150°C Wax 1: 1:2 blend of microcrystalline wax and low density polyethylene resin (trade name: r Hiwax 400PJ), extruder processing temperature: 120°C, die processing temperature: 95°C Wax 2: Volibrobylene wax, Sanyo Chemical product trade name: Viscol 660PJ and polypropylene resin, Mitsui Toatsu Chemical trade name: Mitsui Noblen, 2:3 mixture, extruder processing temperature IAO ℃, die processing temperature 160 ℃ [Effects of the invention] The present invention is a urethane prepolymer or a silyl group-introduced prepolymer. The shape of the so-called moisture-curable reactive hot-melt composition is extremely easy to handle by coating the reactive hot-melt composition with a resin having gas barrier properties through a composite extrusion die. This is a manufacturing method that is simple, improves product storage stability, and allows the use of general-purpose equipment during application.

In particular, as mentioned earlier, in recent years, where reactive hot-melt compositions are increasingly in demand in the market, the processing of product forms for reactive hot-melt compositions has never been more important. According to the present invention, excellent quality stability can be achieved over a long period of time, the required amount can be taken out as needed, and continuous melt supply is possible. This is a product form that can be used, and is highly practical as a new form processing method and storage method for reactive hot melt compositions that have not been possible before.

Claims (5)

[Claims] (1) A kneader-ruder type discharge machine or a twin-screw kneading discharge machine for the purpose of producing and discharging a reactive hot-melt composition, and a single-screw extruder for the purpose of extruding a resin having water vapor gas barrier properties. Alternatively, using a production device in which a twin-screw extruder is connected via a composite extrusion die, the surface of the hot melt composition is coated with a resin having water vapor gas barrier properties to a thickness of 5 to 200 microns. By creating a die structure that can be coated, the hot-melt composition can be continuously coated with a resin having water vapor gas barrier properties to a thickness of 5 to 200 microns, and processed into beads, strands, and pellets. A method for manufacturing and processing a reactive hot-melt composition characterized by: (2) The manufacturing method according to claim 1, wherein a resin selected from polyethylene resin, polypropylene resin, polyvinylidene chloride resin, paraffin wax resin, and natural wax resin is used as the resin having water vapor gas barrier properties. (3) The reactive hot-melt composition contains a urethane prepolymer formed by reacting a hydrocarbon polyol containing hydroxyl groups at both ends, a mixed polyol consisting of a polyether polyol, and a diisocyanate compound, and a thermoplastic rubber component. The manufacturing and processing method according to claim 1, wherein the main component is. (4) The reactive hot-melt composition has the general formula -Si-(Y)3-n (where Y is a hydroxy group, an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, an allyl amino group, an alkylamino group, an oxime 2. The manufacturing and processing method according to claim 1, comprising a silyl group-modified prepolymer resin into which an active silyl group is introduced. (5) A method of filling and packaging the reactive hot-melt composition shaped by the manufacturing method described in claims 1 to 3 into polyethylene bags and storing the same in a paper/cardboard box, with a capacity of 1 to 50. 1 liter polypropylene container and store it in a sealed container, or insert it directly or with a polyethylene bag inside an open steel drum with a capacity of 1 liter to 200 liters, and then replace the container with nitrogen. A method for preserving a reactive hot-melt composition, characterized by preserving the composition in a hermetically sealed manner.