JP2013087172A - Reactive hot-melt adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved hot-melt adhesive composition that has improved storage stability and heat stability of a reactive hot-melt adhesive and quickly promotes a crosslinking reaction of hot melt.SOLUTION: The two-liquid mixing hot-melt adhesive composition comprises a hot-melt adhesive composition A that contains an epoxy group-containing olefin copolymer and a tackifier resin in which the amount of the epoxy group-containing olefin copolymer is 5-90 wt.% based on the total amount of the epoxy group-containing olefin copolymer and the tackifier resin and; a hot-melt adhesive composition B that comprises an epoxy curing agent and an olefin polymer in which the amount of the curing agent is 5-90 wt.% based on the total amount of them. A preferable embodiment includes a two-liquid mixing reactive hot-melt adhesive having a rate of change in melt viscosity of the hot-melt adhesive composition A of within ±20% measured in heating for 24 hours at 180°C and a rate of change in melt viscosity of the hot-melt adhesive composition B of within ±20% measured in heating for 24 hours at 140°C.

Description

  The present invention relates to a reactive hot melt adhesive that is excellent in storage stability and heat stability and exhibits rapid reactivity. More specifically, the present invention relates to a two-component mixed type hot melt adhesive composition that is excellent in storage stability and heat stability and exhibits rapid reactivity.

Hot melt adhesives are generally produced using a stirrer such as a heating mixer or a heating kneader and processed into various shapes. The provided hot melt adhesive is melted in a heating facility such as an applicator or a roll coater, and applied in various shapes.
These hot melt adhesives are used in various fields such as packaging fields such as cardboard boxes and small boxes, sanitary fields such as paper diapers and napkins, bookbinding fields, plywood fields, woodworking fields, automobile fields, home appliance fields, and housing fields. Most used in the field are non-reactive hot melt adhesives. Since such non-reactive hot melt adhesives are mainly composed of ethylene copolymers, styrene block copolymers, and polyolefins, there are limits to the heat resistance temperature and adhesive strength depending on the main components used. .

  Polyurethane-based hot melt adhesives have been most practically used as reactive hot melt adhesives developed to overcome these problems. In the polyurethane hot melt adhesive, the isocyanate group in the component reacts by a moisture curing reaction, and exhibits a tough adhesive force and high heat resistance. However, since this moisture curing reaction proceeds easily in a natural environment, special equipment such as nitrogen replacement of the melting tank is required for storage in a highly confidential container until use. Further, when the polyurethane-based hot melt adhesive is used in an open state, it is necessary to use up the adhesive in a short time, and there is a problem that the remainder when it cannot be used must be disposed of.

Various approaches have been proposed to solve such problems, but none of them are fully satisfactory.
In adhesive applications that require rubber elasticity, Japanese Patent Application Laid-Open No. 62-1774 discloses a polystyrene / polyisoprene / polystyrene block copolymer, or polystyrene / polypropylene, mainly for use in automobile headlamps and rear lamps. There has been proposed a two-component mixed hot melt adhesive comprising a polybutadiene / polystyrene block copolymer mixed with an epoxy resin and a styrene block copolymer mixed with a room temperature curing type curing agent. In this prior art, an improvement in heat resistance and adhesive strength has been proposed by the reaction between an epoxy resin and a room temperature curable curing agent. However, since the epoxy resin is used for the crosslinking reaction, non-hydrogenated styrene has good compatibility. Since the main component is a system block copolymer, the change in melt viscosity is large and the weather resistance is not sufficient at a recommended use temperature of 150 ° C. to 200 ° C.

  Similarly, in applications requiring rubber elasticity, JP-A-9-31428 proposes a two-component mixed hot-melt adhesive composition of an epoxy-modified block copolymer and an epoxy curing agent. Again, a non-hydrogenated styrenic block copolymer is used as the block copolymer, and an epoxy group is introduced into this unsaturated bond, maintaining rubber elasticity and improving adhesion and heat-resistant adhesion. Although it is to obtain a two-component hot melt adhesive that is excellent and excellent in workability, in the illustrated examples, the reactivity is low, and a rapid curing reaction cannot be expected, which is not practical.

  Polyolefin polymers that are chemically stable and high in hardness are used in various fields such as packaging, bookbinding, plywood, and home appliances. For the purpose of improving heat-resistant adhesion, Patent No. 4201858, Patent No. 4422232, etc. describe a reaction comprising a polyolefin copolymer having an epoxy group in the molecule and a rosin (epoxy group curing agent) having a carboxyl group in the molecule. Type hot melt adhesives have been proposed. These prior arts are used in a method in which each component is uniformly mixed at 120 ° C. or less to form a film adhesive, which is sandwiched between substrates and thermocompression bonded. This film adhesive is regarded as a so-called one-component reactive hot melt adhesive, and is used for melting and coating using an apparatus such as an applicator or a roll coater which is a general melt coating apparatus intended by the present invention. The viscosity change when melted cannot be used.

  For similar applications, Japanese Patent Application Laid-Open No. 2000-17242 proposes an ultraviolet irradiation type reactive hot melt adhesive in which a cationic polymerization catalyst is added to polyethylene having an epoxy group. However, a one-component hot melt adhesive using a polymerization catalyst requires a special reaction accelerator in the reaction process and has a problem in long-term storage stability.

JP-A-62-1774 Japanese Patent Laid-Open No. 9-31428 Japanese Patent No. 4201858 Japanese Patent No. 4422232 JP 2000-17242 A

The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems.
The present invention is an improved two-component reactive polyolefin copolymer system that improves storage stability and heat stability, and is a hot melt cross-linking reaction that is a problem of reactive hot melt adhesives. The object is to propose a hot melt adhesive composition.
Another object of the present invention is to provide a two-component reactive hot melt adhesive that can be easily used in melt coating equipment such as applicators and roll coaters that are generally used as hot melt adhesive coating equipment.
Further, since the hot melt adhesive composition A and the composition B proposed in the present invention can be used as a single unreacted hot melt adhesive, the process before the curing reaction is completely completed. However, the present invention proposes an adhesive composition having general performance such as heat resistance that can withstand sufficient use.

  The present invention includes an olefin copolymer having an epoxy group and a tackifier resin, and the olefin copolymer having an epoxy group is 5 to 90 wt% with respect to the total amount of the olefin copolymer having an epoxy group and the tackifier resin. % Hot melt adhesive composition A, an epoxy curing agent, and an olefin polymer, and the epoxy curing agent is 5 to 90% by weight based on the total amount of the epoxy curing agent and the olefin polymer Provided is a two-component mixed hot melt adhesive composition comprising the adhesive composition B.

The two-component mixed hot-melt adhesive composition described above, wherein the hot-melt adhesive composition A has a melt viscosity change rate during heating for 24 hours as shown below within ± 20% when measured at 180 ° C. Is a preferred embodiment of the present invention.
Change rate of melt viscosity (%) = {(melt viscosity after heating for 24 hours−initial melt viscosity) / initial melt viscosity} × 100

  The two-component mixed hot melt adhesive composition described above in which the hot melt adhesive composition B has a change rate of melt viscosity within 24% when heated at 24 ° C. when measured at 140 ° C. is within the range of the present invention. This is a preferred embodiment.

The above-mentioned storage viscosity change rates of the hot melt adhesive composition A and the hot melt adhesive composition B after being left for 30 days at 23 ° C. and 60% RH are within ± 20%. A two-component mixed hot melt adhesive composition is a preferred embodiment of the present invention.
Storage viscosity change rate (%) = {(melt viscosity after storage−initial melt viscosity) / initial melt viscosity} × 100

  The two-component mixed hot melt adhesive composition described above, in which the softening point of the hot melt adhesive composition A and the hot melt adhesive composition B measured by the R & B method is 70 ° C. or higher, is preferably the present invention. It is an aspect.

  The two-component mixed hot-melt adhesive composition described above in which the hot-melt adhesive composition A and the hot-melt adhesive composition B have a gelling coefficient of 180 ° C. or more measured after mixing is preferably 5 or more. It is an aspect.

The present invention provides a reactive hot melt adhesive having improved heat stability and storage stability.
According to the present invention, there is provided a reactive hot melt adhesive composition that is improved in storage stability and heat stability and in which a hot melt crosslinking reaction proceeds rapidly.

  The present invention is a two-component mixture comprising a hot melt adhesive composition A containing an olefin copolymer having an epoxy group and a tackifying resin, and a hot melt adhesive composition B containing an epoxy curing agent and an olefin polymer. A hot melt adhesive composition is provided.

The hot-melt adhesive composition A of the present invention is a hot-melt adhesive composition having a rate of change in melt viscosity at the time of heating for 24 hours shown below as measured at 180 ° C. within ± 20%. preferable. In addition, the hot melt adhesive composition B of the present invention also preferably has a change rate of the melt viscosity at the time of heating for 24 hours as measured at 140 ° C. within ± 20%.
If the rate of change in melt viscosity at the time of heating is within ± 20%, when the hot melt adhesive is melted with an applicator or other device, phenomena such as carbonization, gelation, and decomposition are unlikely to occur, and foreign matters resulting from these Occurrence and application failure can be reduced, and improvement in work efficiency can be expected.

The melt viscosity in the present invention is a melt viscosity measured with an automatic viscometer manufactured by Brookfield (model: BROOKFIELD DV-II + Pro), and when heated for 24 hours, after being continuously heated with the same equipment for 24 hours The melt viscosity of is shown.
The rate of change in melt viscosity is determined from the following formula.
Change rate of melt viscosity (%) = {(melt viscosity at 24 hours continuous heating−initial melt viscosity) / initial melt viscosity} × 100

The hot melt adhesive composition A and the hot melt adhesive composition B of the present invention preferably have a storage viscosity change rate within ± 20% after being left for 30 days in an environment of 23 ° C. and 60% RH. By mixing two components of such hot melt adhesive compositions A and B, the storage stability, which has been a problem with reactive hot melt adhesives, is improved. A sample for measuring the rate of change in storage viscosity is obtained by processing each hot-melt adhesive into a 1 mm sheet and storing it for 30 days under predetermined temperature and humidity conditions.
The storage viscosity change rate is obtained from the following formula.
Storage viscosity change rate (%) = {(melt viscosity after storage−initial melt viscosity) / initial melt viscosity} × 100
If the melt viscosity change rate during storage is within ± 20%, it can be reused without discarding the hot melt adhesive in use or packing it with a special packaging material. Excellent economy.

In the two-component mixed hot melt adhesive composition of the present invention, the 180 ° C. gelling coefficient after mixing of the hot melt adhesive composition A and the hot melt adhesive composition B is preferably 5 or more. The 180 ° C. gelation coefficient refers to a gelation coefficient measured at 180 ° C. by mixing the hot melt adhesive A and the hot melt adhesive B heated to 180 ° C. with the following method. When the gelation coefficient measured at 180 ° C. is 5 or more, the rapid reactivity of the reactive hot melt adhesive can be expressed.
The gelation coefficient in the present invention is a value calculated by the following formula based on the melt viscosity measured with a cone plate type automatic viscometer (model: CV-1) manufactured by MST Engineering Co., Ltd. is there.
Gelation coefficient = 1 / Time from the start of measurement until the melt viscosity doubles (hour)
If the gelling coefficient is 5 or more, it is presumed that the reaction rate when the hot melt adhesive A and the hot melt adhesive B are mixed is extremely fast, and heat resistance is a weak point of the hot melt adhesive in a short time. It shows that it is possible to achieve the improvement.

In the present invention, each of the hot melt adhesive composition A and the hot melt adhesive composition B preferably has a melt viscosity of 1 to 20 Pa · s.
Hot melt adhesives are generally melted and applied in equipment such as applicators and roll coaters. Therefore, if the melt viscosity during use is less than 1 Pa · s, the hot melt adhesive is scattered and porous when applied. There is a possibility that the penetration into the adherend becomes a problem.
Further, when the melt viscosity exceeds 20 Pa · s, the occurrence of stringing and the like is increased, the workability is remarkably lowered, and the fluidity is lowered, so that it is not suitable for intermittent application in a non-contact method.
Moreover, as for the hot-melt-adhesive composition A and the hot-melt-adhesive composition B, it is preferable that the softening point measured by each R & B method is 70 degreeC or more.
When the softening point of the hot melt adhesive is 70 ° C. or less, the adhesives are likely to be blocked with each other in a high temperature environment, and handling may be difficult.

  In the present invention, the hot melt adhesive composition A that can satisfy the requirements for the melt viscosity change rate during 24 hours heating, the storage viscosity change rate after 30 days storage, and the 180 ° C. gelling coefficient after two-component mixing. And a hot melt adhesive composition B comprising a hot melt adhesive composition A containing an olefin copolymer having an epoxy group and a hot melt adhesive composition B containing an epoxy curing agent. Mention may be made of reactive hot melt adhesives.

  The present invention provides a two-component mixed type reactive hot melt adhesive comprising a hot melt adhesive composition A containing an olefin copolymer having an epoxy group and a hot melt adhesive composition B containing an epoxy curing agent. Is also provided.

  The hot melt adhesive composition A, which is a component constituting the two-component mixed hot melt adhesive composition of the present invention, is a hot melt adhesive composition including an olefin copolymer having an epoxy group and a tackifying resin. . The olefin copolymer having an epoxy group is 5 to 90% by weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight, based on the total amount of the olefin copolymer having an epoxy group and the tackifier resin. It is desirable to be contained in.

  The olefin copolymer having an epoxy group of the present invention preferably contains two or more epoxy groups in the molecule, and preferably has an epoxy equivalent of 2000 or less and preferably 1500 or less.

  Examples of the olefin copolymer having an epoxy group used in the present invention include a copolymer of an olefin having about 1 to 4 carbon atoms such as ethylene and propylene and a monomer having a glycidyl group such as a glycidyl (meth) acrylate monomer. A polymer can be mentioned. Such a copolymer may contain other monomer units such as vinyl acetate and alkyl (meth) acrylate. Among these, a binary copolymer of ethylene and glycidyl (meth) acrylate is particularly preferable.

  The tackifier resin used in the hot melt adhesive composition A of the present invention can be appropriately selected from those normally used in hot melt adhesives, but the hot melt adhesive composition A contains an epoxy group. A tackifier resin that has a functional group that undergoes a curing reaction with the olefin copolymer having a function as a curing agent cannot be used. Typical examples of tackifying resins that do not serve as curing agents include hydrogenated terpenes, aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum Examples thereof include resins, coumarone indene resins, and styrene resins. These tackifying resins can be used alone or in combination of two or more.

  A hot melt adhesive composition B containing an epoxy curing agent, which is a component constituting the two-component mixed hot melt adhesive composition of the present invention, comprises an epoxy curing agent and an olefin polymer. It is. The epoxy curing agent is contained in an amount of 5 to 90% by weight, preferably 5 to 70% by weight, more preferably 5 to 50% by weight based on the total amount of the epoxy curing agent and the olefin polymer. desirable. There is no restriction | limiting in particular as an epoxy hardening | curing agent, Although it can select and use suitably from what is normally used as an epoxy hardening | curing agent, the compound which has an acid and an acid anhydride group in a molecule | numerator, a hydroxyl-containing compound, phenol Any one or more epoxy hardeners such as olefins, amines, polyamides, sulfur compounds and the like can be mentioned. The hot melt adhesive composition B is preferably a thermoplastic material containing these epoxy curing agents.

  Epoxy curing agents used in the present invention include primary amines known as room temperature curing types, secondary amines, thiols, tertiary amines known as heat curing types, polyamides, acids and acid anhydrides, Although not limited, such as a hydroxyl group compound and phenols, those containing at least one kind of polymer, oligomer or monomer having any one of these functional groups are preferable.

  The material used as the epoxy curing agent preferably has an acid value, hydroxyl value, or amine value of 150 mgKOH or more.

Specific examples of the curing agent that satisfies the above epoxy curing agent include acids and acid anhydride groups such as maleic acid, malonic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, trimetic acid, and pyromellitic acid. Compounds and compounds having resin acids such as abietic acid, parastrinic acid, and pimaric acid: hydroxyl groups such as compounds having two or more phenolic hydroxyl groups in one molecule such as bisphenol A type novolak resins such as resol type and novolak type Compounds and phenols: aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethyleneaminopropylamine, alicyclic amines such as mensendiamine, isophoronediamine, N-aminoethylpiperazine, m-xylene Diamine, diaminodipheny Aromatic amines such as methane and m-phenylenediamine, polyether polyamines, modified polyamines such as Michael addition polyamines and Mannich addition polyamines: polyamides such as dicyandiamide and aliphatic polyamides; triphenylphosphine, tributylphosphine, tri ( Examples thereof include, but are not limited to, sulfur compounds such as organic phosphine compounds such as p-methylphenyl) phosphine and tri (nonylphenyl) phosphine.
As the epoxy curing agent used in the present invention, acid-modified wax, acid-modified rosin, phenol-modified rosin and polyamides are preferable, and acid-modified rosin and polyamidoamine are particularly preferably used.

The olefin polymer used in the hot melt adhesive composition B of the present invention includes an olefin homopolymer, a copolymer of olefins, and a copolymer of an olefin and a polar monomer.
Examples of these olefin polymers include copolymers of ethylene and α-olefin, ethylene copolymers such as copolymers of ethylene and vinyl acetate, and polar monomers such as alkyl (meth) acrylate; propylene and ethylene And other propylene copolymers such as copolymers with α-olefins; polyethylene known as high density PE, medium density PE, LLDPE, LDPE, propylene homopolymers, random copolymers, block copolymers Examples thereof include polyolefins such as polypropylene known as a polymer.

  The hot melt adhesive composition A and / or B of the present invention may further contain a component that is usually used as a hot melt adhesive. The materials used for these normal hot melt adhesives are not particularly limited as long as they are normally used as hot melt components. Examples of components used in these hot melt adhesives include ethylene copolymers, propylene copolymers, styrene block copolymers, olefins, tackifying resins, waxes, antioxidants, oils, The component chosen from a coloring agent and liquid rubber can be mentioned.

  The ethylene copolymer that may be used in the hot melt adhesive of the present invention is not particularly limited. For example, an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer that is an ethylene copolymer is used. Copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-nbutyl acrylate copolymer, ethylene-1 butene copolymer, ethylene-octene copolymer Etc.

  Examples of the polypropylene copolymer that may be used in the hot melt adhesive of the present invention include a propylene-ethylene copolymer, a propylene-butene copolymer, a propylene-butene-ethylene copolymer, and a propylene homopolymer. Can be mentioned.

  The styrene copolymer that may be used in the hot melt adhesive of the present invention is not particularly limited. For example, hydrogenated polystyrene-polyisoprene-polystyrene copolymer, polystyrene-polybutadiene-polystyrene copolymer. And hydrogenated products.

The tackifying resin that may be used in the hot melt adhesive of the present invention is not particularly limited, but representative examples include rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, alcohol, Rosin derivatives such as rosin esters esterified with glycerin, pentaerythritol, etc., terpene resins such as pinene and pinene, terpene phenol resins, hydrogenated terpenes, aromatic petroleum resins, aliphatic petroleum resins, alicyclics Examples include petroleum resins, copolymerized petroleum resins, coumarone indene resins, styrene resins, and phenol resins. These tackifying resins can be used alone or in combination of two or more.
However, in the hot melt adhesive composition A, a tackifying resin having a functional group used for the epoxy curing reaction cannot be used.

The wax that may be used as a component of the hot melt adhesive of the present invention contributes to the adjustment of the melt viscosity, open time, set time and the like of the hot melt adhesive. Examples of waxes include paraffin wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, atactic polypropylene wax, microcrystalline wax, wood wax, carnauba wax, beeswax, canderia wax, montan wax, and oxides of these waxes, ethylene Examples thereof include acrylic acid copolymer wax, ethylene methacrylic acid copolymer wax, ethylene vinyl acetate copolymer wax, and amide wax.
The wax that can be used as a component of the hot melt adhesive of the present invention is not limited to those exemplified above.
However, the wax having a functional group used for the epoxy curing reaction cannot be used for the hot melt adhesive composition A.

  The oil that may be used as a component of the hot melt adhesive of the present invention is not particularly limited, and examples thereof include process oils composed of a paraffin component, a naphthene component, and an aroma component.

  The liquid rubber that may be used as a component of the hot melt adhesive of the present invention is not particularly limited, and examples thereof include liquid polybutene and liquid polyisobutylene.

  In addition to the hot melt adhesive of the present invention, various additives can be used as necessary, as long as the object of the present invention is not impaired. For example, titanium oxide is used as a colorant, silicone is used as an antiblocking agent, and various antioxidants are used. The antioxidant can prevent thermal degradation and thermal decomposition of the hot melt adhesive. Typical antioxidants are high molecular weight hindered polyphenols, dialkylphenol sulfides, 2, 2'methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6 -Di-tert-butylphenol), 2,6-di-tert-butylphenol-p-cresol, 2,5-di-tert-butylhydroquinone, 2,2,4-trimethyl-1,2-dihydroquinone 2,2,4-trimethyl-1,2-dihydroquinone polymer, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone, nickel dibutyl dithiocarbamate, 1-oxy-3- Methyl-4-isopropylbenzene, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. It is. The additive is desirably contained in an amount of 5 parts by weight or less.

In the hot melt adhesive composition A of the present invention, in addition to the olefin copolymer having an epoxy group and the tackifier resin, the amount of the component that may be further included is the olefin copolymer having an epoxy group and the tackifier. It is desirable that the amount is about 60% by weight or less, preferably about 40% by weight or less based on the total amount of the resin.
In addition, in the hot melt adhesive composition B of the present invention, in addition to the epoxy curing agent and the olefin polymer, the amount of the component that may be further included is 60 with respect to the total amount of the epoxy curing agent and the olefin polymer. It is desirable that the amount be about not more than wt%, preferably not more than about 40 wt%.

  The two-component mixed hot-melt adhesive composition of the present invention can be prepared by mixing the hot-melt adhesive composition A and the hot-melt adhesive composition B constituting it immediately before use. . There is no restriction | limiting in particular in a mixing method, The mixing method according to the usage method of a conventionally well-known hot melt can be selected suitably, and can be used. For example, it is also possible to adopt a method in which the hot melt adhesive composition A and the composition B are made liquid in separate melting tanks and discharged in various forms to mix the liquids. Examples of the discharge form in this case include a spray form, a bead form, a surface form, and a sheet form.

  The mixing ratio of the hot melt adhesive composition A and the hot melt adhesive composition B is such that the hot melt adhesive component A is 50 to 95 parts by weight and the hot melt adhesive component B is 50 to 5 parts by weight. Is preferred.

  It is preferable to mix the above-described hot melt adhesive composition A and composition B with respective melt viscosities of 1 to 20 Pa · s. Therefore, it can implement by selecting suitably the temperature at the time of mixing the hot-melt-adhesive composition A and the hot-melt-adhesive composition B. FIG. For example, when the temperature of the hot melt adhesive composition A is 70 ° C. or higher and the temperature of the hot melt adhesive composition B is 70 ° C. or higher, the liquid materials can be easily mixed with each other. It is.

  In the present invention, the hot-melt adhesive composition satisfying the requirements for the melt viscosity change rate after 24 hours of heating, the storage viscosity change rate after storage for 30 days, the melt viscosity, and the 180 ° C. gelling coefficient after two-component mixing. Using A and hot melt adhesive composition B to obtain an improved reactive hot melt adhesive composition that improves storage stability and heat stability and allows the hot melt crosslinking reaction to proceed rapidly. The most preferred embodiment of the present invention.

  The present invention provides a two-component mixed type reactive hot melt adhesive composition that does not require a special reaction accelerator and solves the problems of conventional hot melt adhesives. Expansion to a wide range of applications such as packaging fields such as small boxes, sanitary materials such as disposable diapers and napkins, bookbinding, plywood, woodworking, automobiles, home appliances, and housing is expected.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

  The physical properties in the present invention were measured by the following methods.

(1) Melt viscosity This is a value measured with an automatic viscometer manufactured by Brookfield (model: BROOKFIELD DVII + Pro). The spindle number of the automatic viscometer used for the measurement was unified to No. 27 and the rotation speed was set to 10 rpm.

(2) Change rate of melt viscosity After measuring the hot melt adhesive composition set at a predetermined temperature with a Brookfield automatic viscometer (model: BROOKFJIELD DV-II + Pro), the melt viscosity after 24 hours of continuous heating was measured. Melt viscosity change rate (%) measured and calculated by the following formula = {(melt viscosity after 24 hours continuous heating−initial melt viscosity) / initial melt viscosity} × 100
The spindle No. used for measurement is No. 27, and the rotation speed is 10 rpm.
The hot melt adhesive composition A was measured at 180 ° C., and the hot melt adhesive composition B was measured at 140 ° C.

(3) Change rate of storage viscosity The melt viscosity of a hot melt adhesive that was allowed to stand for 30 days in an environment of 23 ° C. and 60% RH was measured with a Brookfield automatic viscometer (BROOKFIELD DV-II + Pro). calculate.
Storage viscosity change rate (%) = {(melt viscosity after storage−initial melt viscosity) / initial melt viscosity} × 100
The spindle No. used for measurement is No. 27, and the rotation speed is 10 rpm.
The sample stored for 30 days was a 1 mm sheet.

(4) Gelling coefficient at 180 ° C. After the two-component mixed hot melt adhesive is uniformly mixed, melt viscosity is immediately measured with a cone plate type automatic viscometer (model: CV-1) manufactured by MST Engineering Co., Ltd. The elapsed time until the melt viscosity is doubled is measured and calculated by the following formula.
Gelation coefficient = 1 / Time (time) from the start of measurement until the melt viscosity doubles
The type of cone plate used for the measurement is 100 poise, the rotation speed is 47 rpm, and the measurement temperature is 180 ° C.

(5) Heat-resistant temperature The hot melt adhesive is sufficiently heated and melted with a hand gun (Asahi Melter 70 type) set to a predetermined temperature.
Hot melt adhesive A melts at 180 ° C.
Hot melt adhesive B melts at 140 ° C.
The melted hot melt adhesive is applied to the kraft paper in a 3 g / m bead shape, and the kraft paper is immediately stacked and pressure-bonded with a 1 kg load for 2 seconds.
The test piece was left for 30 minutes in an atmosphere at 23 ° C. and cut to a width of 25 mm.
When mixing the two liquids, apply hot melt adhesive A and hot melt adhesive B, which are sufficiently heated and melted, to the kraft paper at the same ratio so that the bead shape is 3 g / m in total. Crimp for 2 seconds with 1kg load.
The prepared test piece was left in a constant temperature bath at 180 ° C. for 10 minutes, then left in a 23 ° C. atmosphere for 30 minutes and cut to a width of 25 mm as a test piece.
A weight of 100 g is hung on the produced test piece in a peeled shape, and the temperature is increased from 40 ° C. at a rate of 0.5 ° C. per minute.
The temperature at which the weight dropped was expressed as the heat resistant temperature.

(6) Softening point Measured by the R & B method (ring and ball method).
As a device used for the measurement, a ring and ball automatic softening point tester (model: 25D5-ASP-M4SP type) manufactured by Meiho Co., Ltd. is used.
The heating rate during measurement is set to 5 ° C. per minute.

The raw materials used in the present invention are as follows.
a) Ethylene glycidyl methacrylate copolymer (trade name: Bondfast CG5001, manufactured by Sumitomo Chemical Co., Ltd., MFR 380 g / 10 min (190 ° C., 2.16 g load), epoxy equivalent 750)
b) Ethylene vinyl acetate copolymer (trade name: Evaflex EV410, manufactured by Mitsui DuPont Polychemical Co., Ltd., MFR 400 g / 10 min (190 ° C., 2.16 g load), VA content 19% by weight)
c) Ethylene vinyl acetate copolymer (trade name: Ultrasen 735, manufactured by Tosoh Corporation, MFR 1000 g / 10 min (190 ° C., 2.16 g load), VA content 28% by weight)
d) Hydrogenated terpene resin (trade name: Clearon P105, manufactured by Yasuhara Chemical Co., Ltd.)
e) Dicyclopentadiene resin (trade name: ECR5300, manufactured by ExxonMobil)
f) Rosin ester resin (trade name: Pencel GA100, manufactured by Arakawa Chemical Industries, Ltd., acid value 15> mgKOH)
g) Rosin-modified maleic acid resin (trade name: Harimac T80, manufactured by Harima Kasei Co., Ltd., acid value: 170 to 200 mgKOH)
h) High acid value rosin resin (trade name: Pine Crystal KE604B, manufactured by Arakawa Chemical Industries, Ltd., acid value 230-245 mgKOH)
i) Hydrogenated petroleum resin (trade name: Alcon SM10, manufactured by Arakawa Chemical Industries, Ltd.)
j) Polyaminoamide (trade name: Tomide 215X, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 245 mgKOH)
k) Fischer-Tropsch wax (trade name: Sasol Wax H1, Sasol)
l) Paraffin wax (trade name: Paraffin wax 155, manufactured by Nippon Seiwa Co., Ltd.)

Example 1
50 parts by weight of ethylene glycidyl methacrylate copolymer (bond fast CG5001), 50 parts by weight of hydrogenated terpene resin (Clearon P105), and a component uniformly mixed in a melting equipment heated to 160 ° C. It was. Also, 40 parts by weight of ethylene vinyl acetate copolymer (Ultracene 735), 20 parts by weight of polyaminoamide (Tomide 215X), 30 parts by weight of hydrogenated petroleum resin (Alcon SM10), 10 parts of Fischer-Tropsch wax (Sasol H1) A component obtained by uniformly mixing parts by weight with a melting facility heated to 120 ° C. was designated as hot melt adhesive component B.
With respect to the obtained hot melt adhesive component A, the initial melt viscosity at 180 ° C. and the melt viscosity at the time of heating for 24 hours were measured, and the change rate of the melt viscosity at the time of heating for 24 hours was calculated. For the obtained hot melt adhesive component B, the rate of change in melt viscosity when heated at 140 ° C. for 24 hours was calculated. Moreover, about the hot-melt-adhesive component A and the hot-melt-adhesive component B, the storage viscosity change rate after leaving it to stand on 23 degreeC60% RH conditions for 30 days was measured.
80 parts by weight of the hot-melt adhesive component A obtained above and 20 parts by weight of the hot-melt adhesive component B were discharged from a melt tank separately liquefied at the temperature shown in Table 1 to obtain a liquid material About the composition obtained by mixing each other, the 180 degreeC gelation coefficient and heat-resistant temperature were measured.
The respective measurement results are shown in Table 1.

(Example 2)
A component obtained by uniformly mixing 60 parts by weight of Bond Fast CG5001 and 40 parts by weight of Clearon P105 with a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. In addition, hot-melt bonding was performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was set so that the hot melt adhesive component A was 70 parts by weight and the hot melt adhesive component B was 30 parts by weight.
The results of various measurements are shown in Table 1.

(Example 3)
A component obtained by uniformly mixing 60 parts by weight of Bond Fast CG5001, 30 parts by weight of Clearon P105 and 10 parts by weight of Sazol Wax H1 in a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. In addition, hot-melt bonding was performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 90 parts by weight of the hot melt adhesive component A and 10 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

Example 4
A component obtained by uniformly mixing 50 parts by weight of Bond Fast CG5001, 30 parts by weight of Clearon P105, and 20 parts by weight of Sazol Wax H1 with a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. In addition, hot-melt bonding was performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Example 5)
A component obtained by uniformly mixing 60 parts by weight of Bond Fast CG5001, 30 parts by weight of ECR5300, and 10 parts by weight of Sazol wax H1 with a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. In addition, hot-melt bonding was performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Example 6)
A component obtained by uniformly mixing 60 parts by weight of Bond Fast CG5001, 30 parts by weight of Clearon P105, and 10 parts by weight of paraffin wax 155 with a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. In addition, hot-melt bonding was performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Example 7)
A component obtained by uniformly mixing 60 parts by weight of Bond Fast CG5001, 30 parts by weight of Clearon P105 and 10 parts by weight of Sazol Wax H1 in a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. In addition, hot melt bonding is performed by mixing 40 parts by weight of Ultrasen 735, 30 parts by weight of Harimac T80, 20 parts by weight of Pencel GA100, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Example 8)
In Example 7, hot melt adhesive component A and component B were prepared in the same manner as in Example 7 except that the wax of hot melt adhesive component B was changed from sasol wax H1 to paraffin wax 155 ° F. About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 7 was performed.
The results of various measurements are shown in Table 1.

Example 9
40 parts by weight of Bond Fast CG5001, 10 parts of Evaflex EV410, 30 parts by weight of Clearon P105, and 20 parts by weight of Sazol Wax H1 are uniformly mixed in a melting facility heated to 160 ° C. Agent component A. In addition, hot-melt bonding was performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 120 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Example 10)
40 parts by weight of Bond Fast CG5001, 10 parts of Evaflex EV410, 30 parts by weight of Clearon P105, and 20 parts by weight of Sazol Wax H1 are uniformly mixed in a melting facility heated to 160 ° C. Agent component A. In addition, 40 parts by weight of Ultrasen 735, 30 parts by weight of Pine Crystal KE604B, 20 parts by weight of Pencel GA100, and 10 parts by weight of Sazol H1 were mixed uniformly in a melting facility heated to 140 ° C. Adhesive component B was designated.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Comparative Example 1)
A component obtained by uniformly mixing 50 parts by weight of Bond Fast CG5001 and 50 parts by weight of Clearon P105 with a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. Furthermore, 40 parts by weight of Ultrasen 735, 20 parts by weight of Pencel GA100, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 were uniformly mixed in a melting facility heated to 140 ° C. Agent component B.
The hot melt adhesive component A and component B thus obtained are sprayed, beaded, planar, sheeted, etc., and hot melt adhesive component A is applied to 80 parts by weight of hot melt adhesive. The test was carried out with a composition obtained by mixing 20 parts by weight of the agent component B.

(Comparative Example 2)
A component obtained by uniformly mixing 50 parts by weight of Bond Fast CG5001, 30 parts by weight of Pencel GA100, and 20 parts by weight of Sazol Wax H1 with a melting facility heated to 160 ° C. was designated as a hot melt adhesive component A. Furthermore, 40 parts by weight of Ultrasen 735, 20 parts by weight of Pencel GA100, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 were uniformly mixed in a melting facility heated to 140 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

(Comparative Example 3)
2 parts by weight of Bond Fast CG5001, 48 parts of Evaflex EV410, 30 parts by weight of Clearon P105, and 20 parts by weight of Sazol Wax H1 are mixed with a melt equipment heated to 160 ° C. Agent component A. In addition, hot melt bonding is performed by mixing 40 parts by weight of Ultrasen 735, 20 parts by weight of tomide 215X, 30 parts by weight of Alcon SM10, and 10 parts by weight of Sazol H1 in a melting facility heated to 140 ° C. Agent component B.
About the obtained hot-melt-adhesive agent component A and component B, the same measurement as Example 1 was performed. However, the mixing ratio of the hot melt adhesive component A and the component B was 80 parts by weight of the hot melt adhesive component A and 20 parts by weight of the hot melt adhesive component B.
The results of various measurements are shown in Table 1.

As a result of the test, in Examples 1 to 10, the heat stability at the use temperature and the storage stability during storage at 23 ° C. and 60% RH are excellent, the gelation coefficient is high, and the crosslinking reaction proceeds rapidly. It is confirmed that
It can also be confirmed at the heat resistant temperature that the crosslinking reaction proceeds rapidly.
Therefore, it was proved that all of the heating stability, storage stability, and rapid reactivity intended by the present invention were satisfied.

On the other hand, in Comparative Example 1, Comparative Example 2, and Comparative Example 3, it is confirmed that the gelation coefficient after mixing of component A and component B is small and the rapid reaction rate intended by the present invention has not been reached.
Moreover, in the comparative example 2, it is confirmed that the melt viscosity change rate of the component A is high and does not reach the heating stability intended by the present invention.

  From this test result, it was possible to develop a two-component mixed hot melt adhesive composition that is excellent in storage stability and heat stability and in which the crosslinking reaction of the hot melt adhesive proceeds rapidly.

The present invention provides a reactive hot melt adhesive that is excellent in storage stability and heat stability and exhibits rapid reactivity.
The reactive hot melt adhesive provided by the present invention is a two-component mixed hot melt adhesive composition that is excellent in storage stability and heat stability and exhibits rapid reactivity.
The present invention provides a two-component mixed type reactive hot melt adhesive composition that does not require a special reaction accelerator and solves the problems of conventional hot melt adhesives. Expansion to is expected.

Claims (14)

  An olefin copolymer having an epoxy group and a tackifier resin are included, and the olefin copolymer having an epoxy group is 5 to 90% by weight based on the total amount of the olefin copolymer having an epoxy group and the tackifier resin. Hot-melt adhesive composition A comprising hot-melt adhesive composition A, an epoxy curing agent, and an olefin polymer, wherein the epoxy curing agent is 5 to 90% by weight based on the total amount of the epoxy curing agent and the olefin polymer A two-component mixed hot melt adhesive composition comprising the product B. When the hot melt adhesive composition A was measured at 180 ° C., the change rate of the melt viscosity upon heating for 24 hours shown below was within ± 20%, and the melt viscosity measured at 180 ° C. was Brookfield. The two-component mixed hot melt adhesive composition according to claim 1, wherein the composition is 1 to 20 Pa · s as measured with an automatic viscometer manufactured by the manufacturer.
Change rate of melt viscosity (%) = {(melt viscosity after heating for 24 hours−initial melt viscosity) / initial melt viscosity} × 100 When the hot melt adhesive composition B was measured at 140 ° C., the change rate of the melt viscosity upon heating for 24 hours was within ± 20%, and the melt viscosity measured at 140 ° C. was measured by an automatic viscometer manufactured by Brookfield. The two-component mixed hot-melt adhesive composition according to claim 1 or 2, which is 1 to 20 Pa · s as measured.
Change rate of melt viscosity (%) = {(melt viscosity after heating for 24 hours−initial melt viscosity) / initial melt viscosity} × 100 The hot-melt adhesive composition A and the hot-melt adhesive composition B have a storage viscosity change rate shown below within ± 20% after being left for 30 days at 23 ° C. and 60% RH. The two-component mixed hot-melt adhesive composition according to any one of claims 1 to 3.
Storage viscosity change rate (%) = {(melt viscosity after storage−initial melt viscosity) / initial melt viscosity} × 100   The two-component liquid according to any one of claims 1 to 4, wherein the softening points of the hot melt adhesive composition A and the hot melt adhesive composition B measured by the R & B method are both 70 ° C or higher. Mixed hot melt adhesive composition.   The olefin polymer in the hot melt adhesive composition B is at least one selected from an ethylene copolymer, a propylene copolymer, and a polyolefin, according to any one of claims 1 to 5. Two-component mixed hot melt adhesive composition.   The two-component mixed hot melt adhesive composition according to any one of claims 1 to 6, wherein an epoxy equivalent of the olefin copolymer having an epoxy group of the hot melt adhesive composition A is 2000 or less. object.   The epoxy curing agent of the hot melt adhesive composition B is at least one selected from a compound having an acid and an acid anhydride group in its molecule, a hydroxyl group-containing compound, a phenol, an amine, a polyamide, and a sulfur compound. The two-component mixed hot melt adhesive composition according to any one of claims 1 to 7, which is a compound.   The two-component mixed hot-melt adhesive composition according to claim 8, wherein the epoxy curing agent has an acid value, a hydroxyl value, or an amine value of 150 mgKOH or more.   The hot melt adhesive composition A further comprises at least one component selected from waxes, antioxidants, oils, colorants and liquid rubbers. The two-component mixed hot-melt adhesive composition according to any one of the above.   The hot melt adhesive composition B further contains at least one component selected from tackifier resins, waxes, antioxidants, oils, colorants and liquid rubbers. The two-component mixed hot melt adhesive composition according to any one of 1 to 10.   The said hot-melt-adhesive composition A whose temperature is 70 degreeC or more and the said hot-melt-adhesive composition B whose temperature is 70 degreeC or more are mixed, The any one of Claims 1-11 characterized by the above-mentioned. A two-component mixed hot-melt adhesive composition.   The two-component mixed hot-melt adhesive composition according to any one of claims 1 to 12, wherein the hot-melt adhesive component A is 50 to 95 parts by weight and the component B is 50 to 5 parts by weight. The said hot-melt-adhesive composition A and hot-melt-adhesive composition B have the following 180 degreeC gelling coefficient measured after mixing being 5 or more, The two in any one of Claims 1-13 characterized by the above-mentioned. Liquid mixed hot melt adhesive composition.
180 ° C. gelation coefficient = 1 / Elapsed time (time) from the start of measurement until the melt viscosity doubles