JP5013585B2 - Reactive hot melt adhesive composition and bonding method using the same - Google Patents

Description

  The present invention relates to a reactive hot-melt adhesive composition, and more specifically, a moisture-curing type reaction accompanied by a high molecular weight by irradiation with ultraviolet rays in order to increase the initial adhesive strength in a stage before moisture curing. The present invention relates to an adhesive hot melt adhesive composition and an adhesion method using the same.

  Moisture curable reactive hot-melt adhesive composition based on polyurethane prepolymers, including metal materials, wood materials, polymer materials such as plastics and rubber, textile products, natural and synthetic leather products, and paper products Is used in a wide range of fields such as building material panels, automotive interior materials, and clothing. Its characteristic is that it is solvent-free as in the case of a normal hot melt adhesive composition, and the initial adhesive strength is obtained by cooling and solidification. Further, in the time of 24 to 72 hours after bonding, By reacting with moisture, the final adhesive strength and heat resistance higher than those of a normal hot melt adhesive composition are obtained.

  However, since the polyurethane prepolymer lacks thermal stability, the temperature during coating must be 150 ° C. or lower, preferably 140 ° C. or lower. In order to make the upper limit of the viscosity that can be applied under this temperature condition, for example, 100 Pa · s or less, the number average molecular weight (Mn) must be suppressed to 10,000 or less. For this reason, in the conventional polyurethane prepolymer, there was a limit due to the low molecular weight even when the initial adhesive strength was increased.

  As a conventional technique, there is a method using the inherent crystallinity of polyurethane, but in general, the open time is short, the working width becomes narrow, and the adhesive strength is low until crystallization. There is a drawback that it is not necessary to apply a large load until it is done, or equipment improvement such as installation of a forced cooling device is necessary.

Further, as a technique for increasing the initial cohesive force of the adhesive and increasing the initial adhesive strength, a reactive hot melt adhesive composition comprising a polyurethane prepolymer, a thermoplastic resin, and a tackifier is known (for example, Patent Literatures 1 to 3).
Japanese Patent Laid-Open No. 06-122860 JP-A 64-0554089 Japanese Patent Laid-Open No. 52-037936

  However, when the initial adhesive strength is increased by this method, the melt viscosity becomes high and the applicability is remarkably deteriorated. Alternatively, the coating property is improved by increasing the coating temperature (for example, 150 to 180 ° C.), but there is a disadvantage that the thermal stability is extremely inferior. Further, when the melt viscosity is lowered and the applicability is ensured, the ratio of the thermoplastic resin in the adhesive must be reduced, and it is difficult to obtain sufficient initial adhesive strength.

  An object of the present invention is to increase the initial adhesive strength in a stage before moisture curing, with respect to a moisture curing type reactive hot melt adhesive composition mainly composed of a urethane prepolymer.

The present invention comprises [1] a polyurethane prepolymer synthesized from a polyisocyanate, a polyol, and a hydroxyl group-containing (meth) acrylate, containing a (meth) acryloyl group and an isocyanate group at the molecular end as a main component, and a photopolymerization initiator. The polyol composition contains a polyol having a number average molecular weight (Mn) of 10,000 to 100,000 in a proportion of 1 to 20% by weight based on the whole polyol component. The reactive hot melt adhesive composition.
Further, the present invention is [2] above SL [1] to melt the reactive hot-melt adhesive composition according to was applied to an adherend before bonding, by irradiating the pre-ultraviolet coating surface It is the adhesion | attachment method characterized by these.

  As a result of earnest research to achieve the above-mentioned problems, the present inventors have, as a main component, a polyurethane prepolymer containing a (meth) acryloyl group and an isocyanate group at the molecular end, and a reaction containing a photopolymerization initiator. The adhesive hot-melt adhesive composition is applied to the adherend, irradiated with ultraviolet rays before the adherend is bonded, and then bonded to the adherend after it has been polymerized by the radical reaction of the (meth) acryloyl group. It was found that the initial adhesive strength in the stage before moisture curing is increased by performing the above.

  The polyurethane prepolymer used in the present invention comprises a polyisocyanate (A) containing two or more isocyanate groups in one molecule, a polyol (B) containing two or more hydroxyl groups in one molecule, a hydroxyl group and a (meth) acryloyl group. Is synthesized from a hydroxyl group-containing (meth) acrylate (C) containing one or more of each in one molecule.

  Furthermore, the polyol (B) contains at least one polyol having a number average molecular weight (Mn) of 10,000 to 100,000. By using a polyurethane prepolymer containing this polyol, the effect of increasing the molecular weight by irradiation with ultraviolet rays can be increased, and the initial adhesive strength can be increased.

  The proportion of the polyol contained in the polyol (B) is in the range of 1 to 20% by weight. If it is less than 1% by weight, the effect of increasing the molecular weight is small, and if it exceeds 20% by weight, the viscosity of the polyurethane prepolymer becomes too high and the coating property is inferior.

  The (meth) acryloyl group contained at the molecular terminal of the polyurethane prepolymer used in the present invention is 5 to 40 mol% as the number of functional groups with respect to the total terminal functional groups (total of isocyanate groups and (meth) acryloyl groups). It is preferable to contain in the range of 10-30 mol%. When the content of the (meth) acryloyl group is less than 5 mol%, the ratio of high molecular weight due to irradiation with ultraviolet rays decreases and it is difficult to increase the initial adhesive strength. On the other hand, if the content of (meth) acryloyl group exceeds 40 mol%, the ratio of high molecular weight due to irradiation with ultraviolet rays increases so that the tackiness required for adhesion tends to be lost.

  The reactive hot melt adhesive composition of the present invention can realize excellent initial adhesive strength that could not be obtained by conventional reactive hot melt adhesive compositions, and can stabilize adhesive strength and improve productivity. .

  Examples of the polyisocyanate (A) used in the present invention include tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate and the like. And may be used alone or in combination of two or more.

  Furthermore, a biuret type polyisocyanate obtained by reacting the above polyisocyanate with water, an adduct type polyisocyanate obtained by reacting the above polyisocyanate with a polyhydric alcohol such as trimethylolpropane, and the above polyisocyanate isocyanurate. A known polymer such as a multimer obtained by conversion can be used, or a single polymer or two or more of them may be used in combination.

  Examples of the polyol (B) include known ones such as a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyolefin polyol, a polybutadiene polyol, a polyisoprene polyol, and a polycaprolactone polyol, and may be used alone or in combination of two or more. .

  Furthermore, it is essential that the polyol (B) contains at least one polyol having a number average molecular weight (Mn) of 10,000 to 100,000. Examples of the polyol include polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyisoprene polyols, polycaprolactone polyols, and the like, and polyols having a number average molecular weight (Mn) of 10,000 to 100,000. Is mentioned. The number average molecular weight (Mn) is measured with a tetrahydrofuran (THF) solvent using gel permeation chromatography (GPC), and is determined in terms of polystyrene.

  As the hydroxyl group-containing (meth) acrylate (C), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate modified caprolactone , Known ones such as glycidol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like may be used alone or in combination of two or more. In the present invention, (meth) acrylate refers to acrylate or methacrylate.

  In order to contain an isocyanate group at the molecular terminal of the polyurethane prepolymer, the sum of the isocyanate groups of the polyisocyanate (A) should be larger than the sum of the hydroxyl groups of the polyol (B) and the hydroxyl group-containing (meth) acrylate (C). is required.

  In order to contain the (meth) acryloyl group at the molecular terminal of the polyurethane prepolymer, one method is to add a hydroxyl group (afterwards) to the polyurethane prepolymer obtained by reacting the polyisocyanate (A) and the polyol (B). There is a method of reacting (meth) acrylate (C). There is also a method in which a polyol (B) is reacted later with a polyurethane prepolymer obtained by reacting a polyisocyanate (A) with a hydroxyl group-containing (meth) acrylate (C). In both methods, it is necessary to adjust synthesis conditions such as temperature so that the (meth) acryloyl groups do not undergo a polymerization reaction during the reaction.

  When the polyurethane prepolymer is synthesized, the ratio of the total isocyanate groups of the polyisocyanate (A) and the total of the hydroxyl groups of the polyol (B) and the hydroxyl group-containing (meth) acrylate (C) (hereinafter referred to as NCO / OH ratio). The reaction is performed in the range of 1.2 to 3.0, and more preferably in the range of 1.5 to 2.5. This is because the viscosity of the polyurethane prepolymer obtained when the NCO / OH ratio is less than 1.2 becomes too high, and the high molecular weight due to moisture curing is low, and the final adhesive strength and heat resistance cannot be obtained. This is because when 3.0 is exceeded, foaming is remarkably generated during moisture curing.

  The reactive hot melt adhesive composition according to the present invention contains a photopolymerization initiator for facilitating a radical reaction caused by ultraviolet irradiation. Examples of the photopolymerization initiator include known ones such as benzyl dimethyl ketal, benzoin ethyl ether, benzoin isopropyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. These may be used alone or in combination of two or more. As content of a photoinitiator, 0.5-10 weight% with respect to a polyurethane prepolymer, Preferably the range of 1-5 weight% is good.

  Moreover, various additives other than the above can be added as necessary. Examples include known polymerization inhibitors, plasticizers, antioxidants, antifoaming agents, leveling agents, nucleating agents, flame retardants, fillers, tackifying resins, dyes, pigments, ultraviolet absorbers, etc. It may be used alone or in combination of two or more.

The reactive hot melt adhesive composition of the present invention is bonded to an adherend by using an existing coating apparatus typified by rolls and sprays by heating and melting at about 90 to 150 ° C., preferably 100 to 120 ° C. Apply both sides or one side. Next, after irradiating the application surface of the adhesive with ultraviolet rays (for example, 100 to 1,000 mJ / cm ² ), the adherend is bonded. In this case, it is possible to obtain an initial adhesive strength that is better when mechanically crimped. When the crimping is stopped after cooling and solidification, adhesion failure is unlikely to occur. Then, moisture curing proceeds by curing at room temperature (for example, 5 to 35 ° C.) or in a heated and humidified state (for example, 35 ° C. and 80% RH), and the final adhesive strength is obtained.

  The use of the reactive hot melt adhesive composition of the present invention is not particularly limited, but examples include metal materials, wood materials, polymer materials such as plastics and rubber, textile products, natural and synthetic leather products, paper It can be used for bonding products and the like, and the same type and different types of adherends can be bonded.

  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. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

Example 1
The following polyol was charged into a separable flask equipped with a stirrer, a temperature control device, a reflux condenser, a nitrogen inlet tube, and a decompression device. Heating was started while stirring and dehydration was performed at 80 ° C. under reduced pressure.
1,6 Hexanediol, 95 parts of polyester polyol based on adipic acid (functional group number 2.0, Mn3,000)
Polycaprolactone polyol 5 parts (number of functional groups 2.0, Mn 50,000)
Here, Mn is a number average molecular weight, measured with a tetrahydrofuran (THF) solvent using HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation, and determined in terms of polystyrene.

  In a nitrogen atmosphere, 15.0 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 110 ° C. for 1 hour, and further 1.3 parts of 2-hydroxyethyl acrylate was added and reacted at 110 ° C. for 1 hour. . Next, 2.4 parts of 1-hydroxycyclohexyl phenyl ketone was added as a photopolymerization initiator, mixed well, and a reactive hot melt adhesive composition mainly composed of a polyurethane prepolymer (NCO / OH ratio 1.6). , An acryloyl group content of 20 mol%, an active isocyanate group content of 1.4%, a solid at normal temperature (35 ° C. or lower), and a viscosity of 15 Pa · s at 120 ° C. were obtained.

(Example 2)
4,4′-diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 1-hydroxycyclohexyl phenyl so that the same polyol as in Example 1 was blended and the NCO / OH ratio was 1.6 and the content of acryloyl group was 3 mol%. A reactive hot melt adhesive composition was obtained in the same manner as in Example 1, except that the blending amount of the ketone was changed.

(Example 3)
4,4'-diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 1-hydroxycyclohexyl phenyl so that the same polyol as in Example 1 was blended and the NCO / OH ratio was 1.6 and the acryloyl group content was 50 mol%. A reactive hot melt adhesive composition was obtained in the same manner as in Example 1, except that the blending amount of the ketone was changed.

(Comparative Example 1)
Of the polyols used in Example 1, only the polyester polyol was blended, and 4,4′-diphenylmethane diisocyanate, 2-hydroxyethyl so that the NCO / OH ratio was 1.6 and the acryloyl group content was 20 mol%. A reactive hot melt adhesive composition was obtained in the same manner as in Example 1, except that the blending amounts of acrylate and 1-hydroxycyclohexyl phenyl ketone were changed.

(Comparative Example 2)
The same polyol as in Example 1 is blended, 4,4′-diphenylmethane diisocyanate is blended in the same amount as in Example 1, and 2-hydroxyethyl acrylate and 1-hydroxycyclohexyl phenyl ketone are not blended. A reactive hot melt adhesive composition was obtained by the method described above.

  Table 1 summarizes the formulations and resin characteristics of the reactive hot melt adhesive compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

  The adhesive strength of the reactive hot melt adhesive composition of the present invention obtained in Examples 1 to 3 and the adhesive composition obtained in Comparative Example 1 was measured. The measuring method is as follows.

Using a roll coater heated to 120 ° C., it was applied to an olefin sheet with a primer having a width of 25 mm so as to be 100 g / m ² . The coated surface of the adhesive was irradiated with 600 mJ / cm ^{2 of} ultraviolet rays using a metal halide lamp, and the coated surfaces were immediately bonded to each other, and pressed with a press at a pressure of 49 KPa for 10 seconds. The initial peel adhesion strength was measured immediately after completion of the pressure bonding, and the normal peel adhesion strength after curing at 23 ° C. and 50% RH for 4 days. The adhesive strength was measured by T-type peeling at a peeling speed of 50 mm / min. As the breaking state at the time of peeling, B was shown when the material destruction of the olefin sheet with the primer was shown, and C was shown when the cohesive failure of the adhesive composition was shown. The measurement results are shown in Table 2.

  About the adhesive composition obtained by the comparative example 2, it implemented similarly to the above-mentioned measuring method except not irradiating with an ultraviolet-ray. The measurement results are shown in Table 2.

As can be seen from the results in Table 2, the reactive hot-melt adhesive composition of the present invention was irradiated with ultraviolet rays as compared with Comparative Example 2 in which the molecular end of the polyurethane prepolymer did not contain a (meth) acryloyl group. By increasing the molecular weight, the initial adhesive strength increases. Moreover, compared with the comparative example 1 which does not contain the polyol of number average molecular weight (Mn) 10,000-100,000, the effect of high molecular weight by ultraviolet irradiation can be enlarged, and initial adhesive strength can be enlarged. it can. Further, Example 1 in which the content of the acryloyl group was 20 mol% is particularly excellent because it has a higher molecular weight than 3 mol% of Example 2 and is more tacky than 50 mol% of Example 3. Yes.

Claims (2)

An adhesive composition synthesized from polyisocyanate, polyol, and hydroxyl group-containing (meth) acrylate, containing as a main component a polyurethane prepolymer containing a (meth) acryloyl group and an isocyanate group at the molecular end, and containing a photopolymerization initiator. The number average molecular weight of the (meth) acryloyl group is 5 to 40 mol% with respect to the number of terminal functional groups of the entire polyurethane prepolymer, and the polyol has a ratio of 1 to 20 wt% with respect to the entire polyol component. A reactive hot melt adhesive composition comprising a polyol having (Mn) of 10,000 to 100,000. A bonding method comprising melting the reactive hot melt adhesive composition according to claim 1 and applying the composition to an adherend, and irradiating the coated surface with ultraviolet rays before bonding.