JP2010116530A - Two-component reaction type hot melt resin composition and method of application thereof - Google Patents

Abstract

【Task】
Providing a heat-resistant, environment-friendly two-component reactive hot-melt resin composition that is free of gelation due to contact or mixing in the coating device and near the nozzle unit tip when ejection is stopped, and uniform and stable coating and work It is to provide a coating apparatus and a coating method with good performance and maintainability.
[Solution]
[First liquid] and [Second liquid] are brought into contact with each other, and the curing agent or the curing accelerator in [second liquid] permeates the [first liquid] side and the reaction proceeds, and the reaction proceeds. It is a composition. Also, the two-component reaction type hot melt resin composition is injected from different adjacent outlets without being mixed in the apparatus, and the reaction proceeds by contacting or mixing in the air. According to the intermediate shim, the comb-like shim having comb-like grooves at both ends thereof, an independent hot melt supply base having a flow path for supplying the comb-like shim, an air slit shim, an air unit, and a coating method.
[Selection] Figure 1

Description

The present invention relates to a two-component reaction type hot melt resin composition having excellent heat resistance. Further, the present invention relates to a two-component reaction type hot melt coating apparatus and coating method for preventing gelation in the apparatus or at the tip of a nozzle unit when ejection is stopped and forming a uniform and stable coating surface.

In general, adhesives that require heat resistance include, for example, product assembly, solvent-based curable adhesives, solvent-free two-component curable adhesives with room temperature fluidity, and moisture-curable urethane-based hot melts. Adhesives are used.
For example, as a solvent-based curable adhesive, there is a disclosure of a reactive adhesive composition (Patent Documents 1 and 2) containing an olefin copolymer having a carboxyl group in the molecule and an epoxy resin. However, these adhesives are used by dissolving each component in a solvent, and if it stays in the tank for a long time, the carboxyl group and epoxy group react in the melt tank to thicken and gel in the tank. There is a problem that things are likely to stay. In recent years, there is a tendency to be concerned about the use of solvents, such as the need for environmentally friendly adhesives.

When a solventless two-component curable adhesive having room temperature fluidity is used, it is known that it is difficult to achieve both a long open time and a short handling time in order to achieve the required performance.
In addition, the moisture-curing urethane hot melt adhesive has difficulty in stability, and when not used for several days, it is necessary to discard and wash the remaining hot melt adhesive in the applicator melting tank and hose. . There are also known problems such as a long time to reach a sufficiently satisfactory handling strength.

Solvent-free pressure-sensitive adhesive that cures pressure-sensitive hot-melt adhesives based on maleic anhydride-modified SEBS with aluminum chelates to add heat resistance to the ease of handling of pressure-sensitive hot-melt adhesives (Patent Document 3) However, since the curing reaction between the aluminum chelate and maleic anhydride is extremely fast, the viscosity of the hot melt adhesive and the aluminum chelating agent is increased at the instant when the hot melt adhesive and the aluminum chelating agent are mixed. It is practically impossible to apply by adjusting the coating amount.

The epoxidized diene polymer is treated with an aromatic anhydride curing agent under conditions of a polymer / aromatic anhydride molar ratio of 0.5 / 1.0 to 2.0 / 1.0 and a temperature of 100 to 200 ° C. There is a disclosure of a solvent-free pressure-sensitive adhesive (Non-patent Document 1) that is allowed to contact for 6 minutes to 6 minutes to develop a curing reaction. Special equipment to maintain at high temperature is required, and the production speed is remarkably reduced because the curing time becomes longer for use in a practical production line.

Conventionally, as an apparatus and method for applying a two-component adhesive, for example, two types of liquid materials controlled to have a low viscosity are jetted into a mixing chamber immediately before a jet nozzle, mixed, and jetted of a liquid mixture There is a disclosure of a two-liquid mixing type spray device (Patent Document 4) that controls the spray region of the mixed liquid from the left and right with the jet air, but in the device that mixes the two-liquid adhesive in the device before the jetting, the reactive type is particularly effective. In the case of adhesives, depending on the reaction rate of the adhesive, it tends to gel in the device, making it difficult to work for a long time, and it is necessary to clean the inside of the device with one solution at the end of coating. It is mentioned that it is unsuitable for construction. In addition, the two-liquid mixing spray device (Patent Document 5 and Patent Document 6) that sprays the first liquid and the second liquid individually from different nozzles without mixing, and collides and mixes the two liquids that are sprayed in the air. Although there is a disclosure, adhesive remains at the tip of the nozzle when ejection stops, and even if pressurized air is used, it cannot be completely blown away, and the two-part adhesive contacts the nozzle tip when stopped or intermittently applied. In addition, troubles due to gelation and the like are likely to occur, and maintenance is required for each work.

Also, a curtain-shaped spray coating method (Patent Document 7) in which pressurized air from an air ejection hole is applied to a coating material beat from a large number of coating nozzle hole groups to atomize the coating material (Patent Document 7), the first block and the second block A shim plate having a comb-like groove is interposed between the blocks, and the application nozzle hole group is configured by the comb-like groove of the shim plate. The interposed shim plate can be replaced with one having a different thickness. There is a disclosure of a spray coating apparatus (Patent Document 8) of a curtain fiber adhesive that can be freely changed and the cross-sectional area of the coating nozzle hole can be freely changed. Also, the hot melt adhesive is sprayed, which is composed of a flat space that opens to the entire surface with respect to the coating width by providing a pressurized air port adjacent to or close to the adhesive hole where the hot melt adhesive is intermittently supplied. There is a disclosure of a non-contact intermittent spray coating type coating apparatus (Patent Document 9) of a hot melt adhesive that is intermittently coated in a planar shape.
However, for the purpose of uniform coating, these devices constructed by changing the position of the coating nozzle and the air nozzle or the shim plate are known as described above. It is not envisaged to use a reactive hot melt adhesive, and it is not yet sufficient as an apparatus having the desired performance as a two-component reactive hot melt adhesive and the operability to apply.

JP 2002-233501 JP 2003-201459 A Special table 2000-506186 JP-A-11-267554 JP 2001-25689 A JP2007-9403 JP-A-8-243461 JP-A-6-198239 JP-A-11-347459

Shingo Sugiyama, "Latest Technology of Rubber-based Solventless Adhesives" Convertech, 40, (2002.3)

In the present invention, the above problems are solved, and the [first liquid] and [second liquid] applied from different jet nozzles are brought into contact with each other, and the curing agent or the curing accelerator in the [second liquid] is [first liquid]. It is intended to provide a two-component reaction type hot melt resin composition that develops heat resistance and that is easy to handle and environmentally friendly by permeating into the [liquid] side.
Furthermore, the two-component reactive hot-melt resin composition is not gelled by contact or mixing in the coating device and in the vicinity of the nozzle unit tip when ejection is stopped, and uniform and stable coating is possible. It is another object of the present invention to provide a two-component reaction type hot melt coating apparatus and a coating method with good maintainability.

As a result of intensive studies to solve the above problems, the present inventor has found that a two-component reactive hot melt resin composition containing a curing agent or a curing accelerator and a nozzle unit of a two-component reactive hot melt coating apparatus The present invention was completed by finding that the structure and the coating method thereof can achieve the object. The present invention is shown below.

[1] The [first liquid] and [second liquid] applied from different spouts are brought into contact with each other, and the curing agent or the curing accelerator in the [second liquid] permeates the [first liquid] side. A two-component reaction type hot-melt resin composition characterized by reacting at a temperature to give heat resistance.

[2] The [first liquid] according to the above [1] contains the maleic acid-modified polymer (a) as an essential component, and the curing agent as an essential component of the [second liquid] is an epoxy compound (b-1). , [First liquid] or [Second liquid] contains a curing accelerator (c), a two-component reaction type hot melt resin composition.

[3] The [first liquid] described in the above [1] contains the maleic acid-modified polymer (a) and an epoxy compound (b-2) which is a curing agent as essential components, and [second liquid] is a curing accelerator ( A two-component reaction type hot melt resin composition containing c) as an essential component.

[4] The epoxy compound (b-1) according to [2] penetrates into the [first liquid] side and reacts with the maleic acid-modified polymer (a). A two-component reaction type hot melt resin composition having 2 to 20 groups.

[5] A two-component reactive hot melt, wherein the [second solution] according to any one of [1] to [4] is used in a state diluted with a non-reactive diluent. Resin composition.

[6] The [first liquid] and [second liquid] according to any one of [1] to [5] above are jetted from different jet nozzles without being mixed in the apparatus, and a two-liquid reaction A two-component reaction type hot melt coating apparatus characterized by uniformly coating as a hot melt adhesive.

[7] The [first liquid] and [second liquid] according to any one of [1] to [5] ejected from the ejection port simultaneously with the pressurized air are in contact with or mixed in the air. The two-component reactive hot-melt coating apparatus according to [6], wherein the two-component reactive hot-melt adhesive is coated with a two-component reactive hot-melt adhesive characterized in that the reaction proceeds in a uniform phase.

[8] Different jet outlets that jet the [first liquid] and the [second liquid] according to any one of [1] to [5] without mixing in the apparatus are provided in close proximity. The two-component reaction type hot melt coating apparatus according to [6] or [7], wherein the two-component reaction type hot melt adhesive is uniformly coated as a two-component reaction type hot melt adhesive.

[9] A shim group in which the nozzle unit is configured by a comb-shaped shim having comb-shaped grooves at both ends via an intermediate shim, and the [first] according to any one of the above [1] to [5] Liquid] and [Second liquid] are provided through the shim group with an independent hot melt supply base having a flow path for supplying the comb-shaped shim without being mixed, and hot melt supply via the air slit shim. The two-component reaction type hot melt coating apparatus according to any one of [6] to [8], wherein the two-component reaction type hot melt coating apparatus is configured by an air unit provided adjacent to a table.

[10] Pressurized air supplied from an air unit accompanied by an air slit shim is inserted into the comb-shaped groove of the comb-shaped shim 0.3 mm to 2.0 mm from the shim tip of the shim group described in [9]. The two-component reaction type hot melt according to any one of the above [6] to [9], which collides and the height difference between the bottom surface of the air unit and the front end of the shim group is 0 to 0.5 mm. Coating device.

[11] One sheet of intermediate shim provided to prevent the [first liquid] and [second liquid] according to any one of [1] to [5] from being mixed before jetting. [6] to [10], wherein a plurality of sheets can be selected, and the total thickness of the shim group including the intermediate shim and the two comb-shaped shims is 0.2 to 1.5 mm. ] The two-component reaction type hot melt coating apparatus according to any one of the above.

[12] In the shim group composed of an intermediate shim and two comb-shaped shims, the [first liquid] and [second liquid] according to any one of [1] to [5] are injected. Any one of the above [6] to [9], wherein an air port for pressurized air different from the injection port has a structure provided in an intermediate shim or a structure provided by two or more intermediate shims A two-component reaction type hot melt coating apparatus according to claim 1.

[13] In the two-component reaction hot melt coating apparatus according to any one of [6] to [12], [Second liquid] according to any one of [1] to [5]. After stopping the injection first, the [first liquid] according to any one of the above [1] to [5] is stopped after the injection so that the two-component reactive hot melt adhesive is formed at the tip of the nozzle unit. A coating method characterized by not contacting or mixing.

According to the present invention, the [first liquid] and the [second liquid] applied from different nozzles are brought into contact with each other, and the curing agent or the curing accelerator in the [second liquid] permeates the [first liquid] side. Thus, if it is a two-component reaction type hot melt resin composition in which the reaction proceeds, a hot melt adhesive having heat resistance and stable coating performance and good handleability can be obtained.
In addition, the nozzle unit is a comb-shaped shim without mixing the shim group composed of comb-shaped shims having comb-shaped grooves at both ends via an intermediate shim and the two-component reactive hot melt resin composition. A two-component reaction type comprising an air unit provided with an independent hot-melt supply base having a supply flow path through the shim group and adjacent to the hot-melt supply base through an air slit shim Using a hot-melt coating device prevents gelation due to contact or mixing of the two-component reactive hot-melt resin composition at the nozzle unit tip when ejection is stopped, making it a uniform and stable as a two-component reactive hot-melt adhesive Coating is possible. Further, in the case of the coating apparatus according to the present invention, the two-component reactive hot melt resin composition is injected from different adjacent outlets without being mixed in the apparatus, and the reaction proceeds by contacting or mixing in the air. And it can apply uniformly as a two-component reaction type hot melt adhesive without causing poor curing, and desired performance can be obtained.
Furthermore, since gelation hardly occurs in the apparatus and in the vicinity of the tip of the nozzle unit, maintenance such as cleaning at the time of stopping is unnecessary, and there is no clogging at the time of recoating, and workability is good. Therefore, intermittent coating is also possible, and productivity is improved because it is suitable for continuous production.

The nozzle unit disassembled perspective view of the two-pack type adhesive agent coating apparatus which shows the Example of this invention. Similarly nozzle unit assembly perspective view. Similarly longitudinal section Longitudinal sectional view showing another embodiment

Hereinafter, a two-component reaction type hot melt resin composition will be described as an embodiment of the present invention. In addition, although the Example of this invention and a comparative example are given and demonstrated concretely, this is only a mere illustration and this invention is not limited to this, unless the summary is exceeded. In addition, unless otherwise indicated, the part and% in an Example are a mass part and mass%.

The two-component reaction type hot melt resin composition of the present invention may be any one as long as it has a maleic acid-modified polymer (a) as a base polymer and crosslinks with an epoxy compound (b) used as a curing agent. ) May be used to promote the maleic acid / epoxy reaction.

For example, maleic acid-modified polymer (a) is used as an essential component of [first liquid], and epoxy compound (b-1) is used as a curing agent as an essential component for [second liquid]. When the second liquid is brought into contact with the second liquid, the epoxy compound (b-1) in the second liquid permeates into the first liquid and the reaction proceeds. The curing accelerator (c) may be contained in one or both of the [first liquid] and [second liquid].

When the epoxy compound (b-1) described above is used as an essential component of the [second liquid], the molecular weight of the epoxy compound (b-1) is 150 to 1000, and the number of epoxy groups in the molecule is 2 to 20. It is preferable. Examples thereof include Nagase ChemteX Corporation, trade name Denacol EX-314, Toto Kasei Co., Ltd., trade name Epototo YH-300, and the like. An epoxy compound having two epoxy groups in the molecule and having a molecular weight of less than 150 is theoretically manufacturable, but also has problems such as low yield in practical production, and is inferior in practicality as industrialization and suitable. Absent. Moreover, practicality is also difficult for an epoxy compound having more than 20 epoxy groups in the molecule and having a molecular weight of 1000 or less. When the molecular weight exceeds 1000, the penetration rate to the [first liquid] side decreases, and when the number of epoxy groups in the molecule is less than 2, the reactivity as a curing agent is inferior.

Further, for example, maleic acid-modified polymer (a) is used as an essential component of [first liquid] and epoxy compound (b-2) is used as a curing agent, and curing accelerator (c) is used as an essential component in [second liquid]. When the [first liquid] and the [second liquid] are in contact with each other, the curing accelerator (c) in the [second liquid] permeates the [first liquid] side and the reaction proceeds.

When the epoxy compound (b-2) described above is used as an essential component in the [first liquid] together with the maleic acid-modified polymer (a), the number of epoxy groups in the molecule of the epoxy compound (b-2) is 2 to 10 It is preferable that Further, as described in Japanese Patent Application Laid-Open No. 2007-051195 filed by the present applicant, the [first liquid] in which the maleic acid-modified polymer (a) and the epoxy compound (b-2) coexist is melted in the hot melt coating apparatus. In order to be stable at times, the number of epoxy groups in the molecule is 2 to 10, and functional groups that can promote the ring opening of acid anhydrides in the molecule of the epoxy compound, such as hydroxyl groups, nitrogen, etc. It is preferable that it is an epoxy compound whose quantity is 1.0 mass% or less. Examples thereof include Japan Epoxy Resin Co., Ltd., trade name Epicoat 825, Daicel Chemical Industries, Ltd., trade name Celoxide 2021, and the like. When the content of hydroxyl group, nitrogen, etc. exceeds 1.0% by mass, the performance as a reactive hot melt adhesive such as pot life and storage stability tends to be adversely affected.

The epoxy compound (b) used in the present invention may be any conventionally known substance that can be used as the epoxy compound of the present invention. For example, bisphenol type epoxy resin, orthocresol novolak type epoxy resin, phenol novolak type epoxy resin , Cycloaliphatic epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, naphthol type epoxy resin, triphenolmethane type epoxy resin, epoxy modified polybutene, and modified resins thereof, and monomers, oligomers and polymers thereof. These may be used alone or in admixture of two or more.

The maleic acid-modified polymer (a) used in the present invention may be any conventionally known substance that can be used as the maleic acid-modified polymer of the present invention. For example, as a polymer in which maleic acid is modified, a styrene block copolymer , Acrylic block copolymers, random copolymers, amorphous polyolefins and / or crystalline polyolefins, and the like. These may be used alone or in admixture of two or more. A maleic acid-modified polymer having an addition amount of maleic acid of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass is more preferably used. When the addition amount of maleic acid is less than 0.1% by mass, there is a tendency that the reactivity is low and sufficient heat resistance cannot be obtained, and when it exceeds 15% by mass, it is difficult to add maleic acid to the polymer. There is. Specific examples of the maleic acid-modified polymer include Kraton Polymer Japan Co., Ltd., trade name Clayton FG1901X, Asahi Kasei Co., Ltd., trade name Tuftec M1943, and the like.

The curing accelerator (c) used in the present invention has a catalytic action on the reaction between maleic acid and epoxy, for example, 1,8-diaza-bicyclo (5,4,0) undecene-7. Cycloamidine compounds such as 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7, and these compounds Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4 -Compounds having π bonds such as quinone compounds such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin, etc. A compound having an intramolecular polarization formed by adding a tertiary amine compound such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, polyoxyethylene coconut alkylamine, tris (dimethylaminomethyl) phenol, and derivatives thereof, Imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and their derivatives, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, Add organic phosphines such as phenylphosphine, and compounds with π bonds such as maleic anhydride, quinone compounds, diazophenylmethane, and phenolic resins to these organic phosphines. Organophosphorus compounds such as compounds having intramolecular polarization, tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate and other tetra Examples thereof include phenyl boron salts and derivatives thereof. You may use these individually or in combination of 2 or more types. From the viewpoints of safety and low odor, polyoxyethylene coconut alkylamine and dimethyldodecylamine are more preferable.

The [first liquid] of the present invention may contain a tackifying resin as necessary, and is not particularly limited. For example, there are terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone / indene resins, rosin resins, and derivatives thereof, which are used alone or in combination of two or more. May be used. Specific examples include Yasuhara Chemical Co., Ltd. and trade name Clearon M115.

Further, the [first liquid] of the present invention may contain a plasticizer as needed, and is not particularly limited. For example, there are process oil and / or polyolefin fluid and / or wax, and these may be used alone or in combination of two or more. Specific examples include Idemitsu Kosan Co., Ltd., trade name process oil PW32.

Furthermore, you may add suitably conventionally well-known antioxidant, for example, a hindered phenol etc. in the [first liquid] of this invention in the range which can be used. In addition, a conventionally known filler such as calcium carbonate may be appropriately added within a usable range.

In the [second liquid] of the present invention, a curing agent or a curing accelerator may be used alone or diluted to a non-reactive diluent. The non-reactive diluent used in the [second liquid] is not particularly limited as long as it does not react with the curing agent or the curing accelerator. For example, water, an organic solvent that does not adversely affect the environment, a hot melt resin composition, and the like can be given.

When a hot melt resin composition is used as the non-reactive diluent used in the [second liquid] of the present invention, it is not particularly limited, but conventionally known EVA-based, rubber-based, amorphous / crystalline polyolefin-based A hot melt resin composition can be used. The preparation of the hot melt resin composition is not particularly limited as long as it is a conventionally known method. For example, in a melting / dissolving tank such as a heating type melting stirring tank, preferably in a vacuum, under a nitrogen stream, at a normal temperature of 150 ° C. to 250 ° C. For example, a method of melting and mixing with heating by using a rotating blade, a method of melting and mixing with a screw of a single or twin screw extruder, and the like.

The [first liquid] and the [second liquid] can be applied by a conventionally known method of applying from different jet nozzles. For example, a normal application for applying a hot melt resin composition, a spraying device for applying a liquid material, a production apparatus for a spunbond nonwoven fabric or a melt blown nonwoven fabric, and the like can be used. Examples of the method of bringing the [first liquid] and the [second liquid] into contact after coating include combining the above-described coating facilities or using a special coating nozzle. As a combination method, for example, after the [first liquid] is applied to the substrate, the [second liquid] is applied thereon. Alternatively, after the [second liquid] is applied to the substrate, the [first liquid] is applied from above. [First liquid] and [second liquid] are brought into contact in the air immediately after application to land on the substrate. For example, the [first liquid] is applied to a base material, and the [second liquid] applied to another base material is bonded. When the [second liquid] contains a non-volatile non-reactive diluent such as a hot-melt resin composition, the two-component reactive hot-melt resin composition of the present invention is used for joining the base material A and the base material B. In order to exhibit heat resistance when a force in the peeling direction is applied to the base material A and the base material B, the [second liquid] is applied so as not to cover the entire surface of the [first liquid]. In particular, it is sufficient that the [first liquid] has a continuous layer connecting the base material A and the base material B. Examples of the application pattern of [first liquid] and [second liquid] include a sheet shape, a fiber shape, a spiral shape, a bead shape, and a dot shape. As for the special application nozzle, discharge ports for individually applying different kinds of liquid substances or melts are arranged on the same die, and a conventionally known apparatus can be used.

In order to more suitably obtain the performance of the two-component reaction type hot melt resin composition of the present invention, it is preferable to carry out the coating apparatus and the coating method of the present invention. Hereinafter, as an embodiment of the present invention, a coating apparatus and a coating method will be described with reference to the drawings. In addition, although the Example of this invention and a comparative example are given and demonstrated concretely, this is only a mere illustration and this invention is not limited to this, unless the summary is exceeded. Moreover, although the mixing | blending and manufacturing method of a two-component reaction type hot-melt resin composition used in an Example etc. are shown below, it is not limited to this. In addition, the A liquid and B liquid in an Example are the code | symbol shown for convenience, and A liquid and B liquid are [1st liquid] or [2nd liquid] unless there is particular notice.

Referring to FIG. 1, the nozzle unit 6 of the coating apparatus includes a left air unit 1A, a left air slit shim 2A, a left hot melt supply base 3A, a left comb shim 4A, an intermediate shim 5, a right comb shim 4B, and a right A hot melt supply base 3B, a right air slit shim 2B, and a right air unit 1B are formed. A liquid injection port 7A is formed between the left hot melt supply base 3A and the intermediate shim 5 via a left comb shim 4A. A left air unit 1A with a left air slit shim 2A for supplying pressurized air A is provided adjacent to the left hot melt supply base 3A, and a right comb shim 4B is provided between the right hot melt supply base 3B and the intermediate shim 5. A right air unit 1B with a right air slit shim 2B for supplying pressurized air B is provided adjacent to the right hot melt supply base 3B.

The pressurized air A injected from the left air unit 1A accompanied by the left air slit shim 2A collides with the comb-shaped groove of the left comb-shaped shim 4A forming the A liquid injection port 7A, and from the injection port 7A together with the A liquid. The pressurized air B ejected toward the coating surface and ejected from the right air unit 1B accompanied by the right air slit shim 2B collides with the comb-shaped groove of the right comb-shaped shim 4B forming the B liquid ejection port 7B. , And B liquid are ejected from the ejection port 7B toward the coating surface.

Pressurized air A injected from the left air unit 1A associated with the left air slit shim 2A or pressurized air B injected from the right air unit 1B associated with the right air slit shim 2B is left via the intermediate shim 5. It is preferable to collide with a comb-shaped groove on the inner side of 0.3 mm to 2.0 mm from the tip of the shim group constituted by the comb-shaped shim 4A or the right comb-shaped shim 4B. The scavenging effect of the hot melt resin composition is high, there is no dispersion of the pressurized air flow, and it is difficult to cause resin accumulation. In particular, in the case of a reactive hot melt resin composition, when the ejection is stopped, each hot melt resin composition of the A liquid or B liquid remaining in the vicinity of the ejection outlet 7A or 7B is scraped out by pressurized air. Stable coating properties can be achieved without causing gelation, which is the object of the invention. When pressurized air exceeds the range of 0.3 mm to 2.0 mm from the tip of the shim and collides with or cannot collide with the comb-shaped grooves, the compressed air flow is dispersed and effective for the hot melt resin composition. As a result, the hot melt resin composition stays at the tip of the nozzle unit and the vicinity of the nozzle and gels, making re-coating impossible and obtaining a uniform coating surface, etc. Productivity decreases, and maintenance such as cleaning is required every time supply is stopped, resulting in reduced workability.

Furthermore, the bottom surface of the left air unit 1A accompanied by the left air slit shim 2A, the tip of the shim group formed by the left comb-shaped shim 4A and the intermediate shim 5, or the bottom surface of the right air unit 1B accompanied by the right air slit shim 2B And the right comb-shaped shim 4B and the shim tip formed by the intermediate shim 5 are preferably 0 to 0.5 mm in height, and if within this range, the liquid A or B near the injection port 7A or 7B The contact efficiency of the liquid hot melt resin composition is improved, the reaction is started without causing poor curing, the desired adhesive performance is exhibited, and the uniform coating performance, which is the object of the present invention, can be achieved. When the height difference exceeds 0.5 mm, the convection of the pressurized air is poor, and the two-component hot melt resin composition near the tip of the nozzle unit and the injection port is brought into contact without being jetted or subjected to gelation. Uniform coating surface cannot be obtained due to the dispersion of compressed air.

The intermediate shim 5 provided to block the mixing of the two-component hot-melt resin composition can be freely selected and may be composed of one or a plurality of sheets. Further, the comb-shaped shims 4A and 4B are not limited in the width or pattern of the comb-shaped grooves, and may be composed of one sheet or a plurality of sheets.
However, the total thickness of the intermediate shim 5 and the shim group composed of comb-shaped shims 4A and 4B at both ends thereof is preferably 0.2 to 1.5 mm. The melt resin composition does not contact or mix before jetting, and the progress of the reaction due to the contact or mixing of the hot melt resin composition in the air after jetting is not hindered. If the total thickness of the shim group exceeds 1.5 mm, the pressurized air after injection is less likely to act efficiently, preventing contact or mixing of the hot melt resin composition in the air. The melt resin composition remains and a stable and uniform coated surface cannot be obtained, such as causing poor curing. In addition, when the total thickness of the shim group is less than 0.2 mm, the intermediate shim or comb shim becomes very thin, so that disassembly and cleaning becomes extremely difficult. In addition, since the shim is thin, industrial production is difficult from the viewpoint of insufficient strength of the shim and the need for advanced technology for processing the comb-shaped grooves.

The two-component reaction type hot melt resin composition is injected without being mixed in the apparatus, and is different from the injection action to the hot melt resin composition in order to prevent the adhesive from staying at the tip of the nozzle unit. Uniform and stable coating can be performed by providing a compressed air flow path as an air port 8 in the intermediate shim 5 or by forming a compressed air flow path between a plurality of stacked intermediate shims. Is possible.

When the injection is stopped in the application of the two-component reactive hot melt resin composition in which the reaction proceeds by the penetration of the curing agent or the effect accelerator in the [second solution] into the [first solution] side. Preferably, the injection of the [second liquid] is stopped first, and then the injection of the [first liquid] is stopped. Since the curing agent or the effect accelerator in the [second liquid] does not stay at the tip of the nozzle unit, the curing reaction does not proceed and gelation can be prevented.

The two-component reaction type hot melt resin composition, the two-component reaction type hot melt coating apparatus and the coating method thereof according to the present invention can be used for adhesive products such as assemblies, tapes, sealants, and the application and processing thereof. However, it is not limited to these.

Each evaluation method of the two-component reaction type hot melt resin composition used in the examples and comparative examples and the coating stability evaluation of the coating apparatus are as follows.

Heat resistance: The heat resistance evaluation method of the two-component reaction type hot melt resin composition coated with [first liquid] and [second liquid] was performed by a SAFT (shear bond fracture temperature) test. A test piece is obtained by coating a PET film with a two-component reaction type hot melt adhesive to a thickness of 50 μm and curing the test piece. The test piece has a width of 25 mm and a length of 25 mm on the evaluation plate (SUS plate) with a load of 2 kg. The roll was reciprocated twice for pressure bonding. As the evaluation conditions, at a measurement temperature from room temperature to 180 ° C., a load of 100 g was applied in the shear direction, the temperature was raised at 2 ° C./5 minutes, and the drop temperature of the weight was measured.

Penetrability (ATR measurement): The penetrability (penetration rate) of the [second liquid] epoxy compound or curing accelerator to the [first liquid] side was evaluated by infrared absorption measurement. The release melt PET film was coated with the hot melt resin composition [first liquid] so as to have a thickness of 50 μm, and the epoxy compound or curing accelerator as [second liquid] was applied thereon and cured. Thereafter, the hot-melt resin composition is peeled off from the release PET film, and the surface on the release PET film side of the coating film is [second liquid] by ATR measurement (multiple reflection measurement: manufactured by JASCO Corporation). By measuring the change in the peak intensity derived from the epoxy compound or the curing accelerator, it was evaluated as the permeability of the [second liquid] from the coating surface. In the case of the epoxy compound (b), the change in peak intensity derived from the epoxy compound, and in the case of the curing accelerator (c), maleic anhydride is ring-opened by the curing accelerator to become a carbonium ion COO- The decrease in peak intensity in the vicinity of C═O (1780 cm ⁻¹ ) derived from maleic anhydride was measured.

Long-term stability: The long-term stability of a single composition of [First liquid] and [Second liquid] was evaluated. [First liquid] and [Second liquid] Each resin composition was prepared, and each resin composition was allowed to stand in an aluminum bag at 23 ° C. for 7 days, and then the viscosity was measured. The viscosity was compared.

Continuous coating property: [First liquid] and [Second liquid] were applied using a coating apparatus, and the state of the nozzle unit tip and the vicinity of the injection port after one hour of continuous coating was examined. `` Good '' if continuous coating is possible and there is no dirt or clogging and the equipment is stable, continuous coating is possible, but dirt or clogging is seen and adhesive is scattered "No", continuous coating is impossible, and those with a lot of dirt and clogging are marked "No".

Re-coating property: After applying continuously for 1 hour, stop the device as it is, and check the state of the nozzle unit tip and the vicinity of the injection port when re-coating is started 24 hours later. evaluated. The coating that can be started without any problem and stable is judged as “good”, and the gelation caused clogging, and the coating that cannot be applied again is marked as “impossible”.

Coating surface: Check the coating state of the two-component reaction type hot melt resin composition, “good” if the coating is uniformly applied, “impossible” if the coating surface is uneven, and hot melt lumps are seen "

Hereinafter, the blending of the two-component reaction type hot melt resin composition used in Examples and Comparative Examples is described in Examples 1 to 4 and Comparative Examples 1 to 3, and Examples 5 to 5 are applied to coating apparatuses and coating methods. Examples are shown in Example 6 and Comparative Examples 4 to 9.

[First liquid]: Maleic acid-modified polymer (a) (manufactured by Kraton Polymer Japan Co., Ltd., trade name: Kraton FG-1901X), tackifier resin (manufactured by Yashara Chemical Co., Ltd., trade name: YS Resin TO-105) ) 150 parts by mass, 60 parts by mass of process oil (trade name PW-32, manufactured by Idemitsu Kosan Co., Ltd.), 1.5 parts by mass of antioxidant, 5 parts by mass of curing accelerator (c) (dimethyldodecylamine) [No. Two-component]: Epoxy compound (b-1) (manufactured by Nagase ChemteX Corporation, trade name Denacol EX-314) 100 parts by mass, ethanol 100 parts by mass [first liquid] and [second liquid], respectively, with a kneader It knead | mixed or stirred with the mixer and adjusted.

[First liquid]: Maleic acid-modified polymer (a) (manufactured by Kraton Polymer Japan Co., Ltd., trade name: Kraton FG-1901X), 100 parts by mass, epoxy compound (b-2) (manufactured by Japan Epoxy Resin Co., Ltd., trademark) Name Epicoat 825) 10 parts by mass, tackifier resin (Yasuhara Chemical Co., Ltd., trade name: YS Resin TO-105) 150 parts by mass, process oil (Idemitsu Kosan Co., Ltd., trade name PW-32) 60 parts by mass , 1.5 parts by weight of antioxidant [second liquid] curing accelerator (c) (dimethyl dodecylamine) 100 parts by weight, 400 parts by weight of ethanol [first liquid] and [second liquid] are kneaded with a kneader, Or it stirred with the mixer and adjusted.

The same adjustment as in Example 1 was performed except that the epoxy compound (b-1) of [Second liquid] was changed to BF-1000 (manufactured by ADEKA Corporation) in Example 1.

[First liquid]: 100 parts by mass of maleic acid-modified polymer (a) (trade name, Kraton FG-1924, manufactured by Kraton Polymer Japan Co., Ltd.), tackifying resin (trade name, Clearon P-125, manufactured by Yashara Chemical Co., Ltd.) 200 parts by mass, plasticizer (trade name Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.), 100 parts by mass, curing accelerator (dimethyldodecylamine) 3 parts by mass [second liquid]: non-reactive polymer (Clayton polymer) Japan Co., Ltd., trade name: Kraton G-1652 100 parts by weight, tackifier resin (Yasuhara Chemical Co., Ltd., trade name Clearon P-125) 150 parts by weight, plasticizer (Idemitsu Kosan Co., Ltd., trade name) Process oil PW-90) 30 parts by mass, curing accelerator (c) (manufactured by NOF Corporation, trade name: Epiol G-100) 60 parts by mass [first liquid] Beauty the second liquid] was melt-kneaded respectively kneader to prepare a hot-melt resin composition.

The compressed air collides with the comb-shaped groove of the comb-shaped shim 0.1 mm inside from the front end of the shim group, and the height difference between the bottom surface of the air unit and the front end of the shim group is 0 mm, and the thickness of the shim group is 0 Using a coating apparatus having a nozzle unit of 3 mm, the [first liquid] and [second liquid] of Example 4 were applied, and after stopping the [second liquid] ejection, the [first liquid] was ejected. Stopped.

Coating was performed in the same manner as in Example 1 except that a pressurized air port was provided in the intermediate shim.

(Comparative Example 1)
Prepared in the same manner as in Example 1 except that [Second liquid] was not used in Example 1.

(Comparative Example 2)
The same adjustment as in Example 1 was carried out except that the curing accelerator (c) (dimethyldodecylamine) of Example 1 [first liquid] was not used.

(Comparative Example 3)
The same adjustment as in Example 2 was performed except that [Second liquid] was not used in Example 2.

(Comparative Example 4)
Coating was performed in the same manner as in Example 5 except that the pressurized air did not collide with the comb-shaped grooves of the comb-shaped shim and contacted the [first liquid] and [second liquid] of Example 4 outside the apparatus. .

(Comparative Example 5)
Coating was performed in the same manner as in Example 5 except that the pressurized air collided with the comb-shaped grooves of the comb-shaped shims 2.1 mm inside from the front end of the shim group.

(Comparative Example 6)
Coating was performed in the same manner as in Example 5 except that the height difference between the bottom surface of the air unit and the shim group was 1.0 mm.

(Comparative Example 7)
Coating was performed in the same manner as in Example 5 except that the thickness of the shim group was 1.8 mm.

(Comparative Example 8)
Coating was performed in the same manner as in Example 5 except that the ejection of [first liquid] and [second liquid] was stopped simultaneously.

(Comparative Example 9)
Using the coating apparatus described in Patent Document 2, [First Liquid] and [Second Liquid] of Example 4 were applied.

The heat resistance evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.
Note specimens After drying the the first liquid] was 50μm applied onto a PET film, ethanol and on to the second liquid] to 2.0 g / ^{m 2} coating thereof, 1,3 at 50 ° C. It was cured by curing for 7 days.

The permeability (ATR measurement) evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 2 (epoxy compound penetration) and Table 3 (curing accelerator penetration).
In addition, in order to confirm that the epoxy compound or the curing accelerator penetrates into the [first liquid], the [first liquid] is applied to the release PET film by 50 [mu] m, and then the [second liquid]. The solution] was applied at 2.0 g / m ² and the ethanol was dried, followed by curing at 50 ° C. for 1, 3, 5 and 7 days, and the coating film peeled off from the release PET film was measured.

As a method for confirming the penetration of the epoxy compound shown in Table 2, in the case of Denacol EX-314 used in Example 1, a characteristic peak around 1100 cm ⁻¹ was used as an index, and BF− used in Example 3 was used as an index. In the case of 1000, a characteristic peak around 900 cm ⁻¹ was used as an index. In the table, in order to clarify the difference in the amount of the penetrated epoxy compound, all the epoxy compounds in [Second liquid] penetrated into [First liquid] and were uniformly dispersed in the coating film. The peak intensity of the epoxy compound of 1 was taken as 1, and the peak intensity ratio relative thereto was shown. The test piece in which all of the epoxy compound in [Second liquid] penetrated [First liquid] and was uniformly dispersed in the coating film was coated with 50 μm of [First liquid] on the release PET film. [Second liquid] was applied at 2.0 g / m ² , ethanol was dried, and the resin composition coating film peeled off from the release PET film was dissolved in toluene and stirred uniformly. The film was applied on the film so as to have a thickness of 50 μm. The coating film in a state where all of the [second liquid] epoxy compound was infiltrated into the [first liquid] and uniformly dispersed was measured by ATR measurement, and the peak intensity of the obtained epoxy compound was set to 1.

The long-term stability evaluation results of Examples 1 to 2 are shown in Table 4.

The heat resistance and coating stability evaluation results of Examples 5 to 6 and Comparative Examples 4 to 9 are shown in Table 5.

In Examples 1 to 3 of the present invention, heat resistance was improved with the reaction during curing as shown in Table 1, compared with Comparative Examples 1 to 3. Further, from the results of Tables 2 and 3, it is clear that the epoxy compound or curing accelerator contained in [Second liquid] penetrates [First liquid]. In Table 2, when Example 1 and Example 3 were compared, the penetration rate of an epoxy compound having a large molecular weight tends to be slow, and an epoxy compound having an average molecular weight of 1000 or less is effective from the viewpoint of penetration rate. all right.

In Examples 5 to 6 of the present invention, as shown in Table 5, since the heat resistance performance of the two-component reactive hot melt adhesive coating is good, the two-component reactive hot melt resin composition is A coating film is formed by being uniformly dispersed, indicating that the curing reaction is in progress. On the other hand, in Comparative Example 6 using the coating apparatus described in Patent Document 2, since the cohesive failure occurs in the heat resistance evaluation and the heat resistance is poor, the dispersibility of the two-component reaction type hot melt resin composition is poor and the curing is poor. Indicates that this is happening. Therefore, it was found that the two-component reaction type hot melt coating apparatus having the nozzle unit shown in the present invention is effective for application of the two-component reaction type hot melt resin composition.

From the above results, the [first liquid] and [second liquid] of the two-component reaction type hot melt resin composition of the present invention are contacted after application, and the curing agent or the curing accelerator in the [second liquid] It was found that a two-component reaction type hot melt resin composition having heat resistance and excellent long-term stability and workability can be obtained by permeating into the [first liquid] and proceeding with the reaction. Further, by using the two-component reaction type hot melt coating apparatus of the present invention, the two-component reaction type hot melt resin composition is injected without being mixed in the apparatus, and is effectively contacted or mixed in the air. It has been found that the curing reaction proceeds, the desired adhesive performance is expressed, and uniform and stable coating is possible. In particular, in the coating method of the two-component reaction type hot melt resin composition, it was possible to perform more stable coating without advancing the curing reaction by stopping the jetting first.

The present invention relates to a two-component reactive hot melt resin composition, a two-component reactive hot melt coating apparatus and a coating method according to the present invention. For example, a two-component reactive hot melt composition is applied using the coating apparatus of the present invention. Thus, the composition and performance that cause inconvenience by mixing the two liquids in advance, or the work can be applied and produced more easily and more stably than in the past. The product can be obtained.

1A Left air unit 1B Right air unit 2A Left air slit shim 2B Right air slit shim 3A Left hot melt agent supply base 3B Right hot melt supply base 4A Left comb shim 4B Right comb shim 5 Intermediate shim 6 Nozzle unit 7A A liquid Injection port 7B B liquid injection port 8 Air port

Claims (13)

[First liquid] and [second liquid] applied from different spouts are brought into contact, and the curing agent or the curing accelerator in [second liquid] reacts by penetrating into the [first liquid] side. A two-component reaction type hot melt resin composition characterized by having heat resistance. The [first liquid] according to claim 1 comprises maleic acid-modified polymer (a) as an essential component, and the curing agent as an essential component of [second liquid] is an epoxy compound (b-1), Liquid] or [Second liquid] contains a curing accelerator (c), a two-component reaction type hot melt resin composition. The [first liquid] according to claim 1 contains the maleic acid-modified polymer (a) and the epoxy compound (b-2) which is a curing agent as essential components, and the [second liquid] essential as a curing accelerator (c). A two-component reactive hot melt resin composition as a component. Since the epoxy compound (b-1) according to claim 2 penetrates into the [first liquid] side and reacts with the maleic acid-modified polymer (a), the molecular weight is 150 to 1000, and the number of epoxy groups in the molecule is 2 to 2 A two-component reaction type hot-melt resin composition characterized by comprising twenty. A two-component reactive hot melt resin composition, wherein the [second liquid] according to any one of claims 1 to 4 is used in a state diluted with a non-reactive diluent. The [first liquid] and [second liquid] according to any one of claims 1 to 5 are jetted from different jet nozzles without being mixed in the apparatus, and are two-component reactive hot melt bonding A two-component reaction type hot melt coating apparatus characterized by uniformly coating as an agent. The [first liquid] and [second liquid] according to any one of claims 1 to 5, which are injected from the injection port simultaneously with the pressurized air, become a homogeneous phase by contacting or mixing in the air. The two-component reaction type hot melt coating apparatus according to claim 6, wherein the reaction proceeds in a two-component reaction type hot melt adhesive. It has the structure where the different jet outlet which injects without mixing [first liquid] and [second liquid] as described in any one of Claims 1-5 within an apparatus adjacently. The two-component reaction type hot melt coating apparatus according to claim 6 or 7, wherein the two-component reaction type hot melt adhesive is uniformly coated. The nozzle unit is a shim group including comb-shaped shims having comb-shaped grooves at both ends thereof via an intermediate shim, and the [first liquid] and the [first liquid] according to any one of claims 1 to 5; An independent hot melt supply base having a flow path for supplying the second liquid] to the comb-shaped shim without being mixed is provided via the shim group, and is adjacent to the hot melt supply base via the air slit shim. The two-component reaction type hot melt coating apparatus according to any one of claims 6 to 8, wherein the two-component reaction type hot melt coating apparatus is configured by an air unit provided. Pressurized air supplied from an air unit accompanied by an air slit shim collides with a comb-shaped groove of a comb-shaped shim 0.3 mm to 2.0 mm from the shim tip of the shim group according to claim 9, and The two-component reaction type hot melt coating apparatus according to any one of claims 6 to 9, wherein a difference in height between the bottom surface of the air unit and the front end of the shim group is 0 to 0.5 mm. An intermediate shim provided to prevent the [first liquid] and [second liquid] according to any one of claims 1 to 5 from being mixed before jetting is selected as a single sheet or a plurality of sheets. The total thickness of the shim group which is free and is constituted by the intermediate shim and the two comb-shaped shims is 0.2 to 1.5 mm. 11. The two-component reaction type hot melt coating apparatus according to Item. In the shim group composed of an intermediate shim and two comb-shaped shims, the injection port for injecting the [first liquid] and [second liquid] according to any one of claims 1 to 5 The air port for different pressurized air has a structure provided in an intermediate shim, or a structure provided in two or more intermediate shims. Two-component reaction type hot melt coating device. The two-component reaction type hot melt coating apparatus according to any one of claims 6 to 12, wherein the injection of the [second liquid] according to any one of claims 1 to 5 is stopped first. After that, by stopping the injection of the [first liquid] according to any one of claims 1 to 5, the two-component reactive hot melt adhesive does not contact or mix at the tip of the nozzle unit. A characteristic coating method.