JPH06271834A - Moisture-curing type reactive hot-melt adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent workability, adhesiveness and heat resistance and also low toxicity. CONSTITUTION:This adhesive composition is obtained by blending (A) 100 pts.wt. of a polymer having hydrolyzable silicon-containing functional group with (B) 30-200 pts.wt. of a resin for providing solidification at normal temperature and (C) 0.1-20 pts. wt. of a silanol condensation catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable reactive hot-melt adhesive composition, and more particularly to a moisture-curable reactive hot-melt adhesive which is excellent in workability, adhesiveness and heat resistance and is less toxic. Agent composition.

[0002]

2. Description of the Related Art Generally, hot-melt adhesives are fast in bonding speed, automated in production lines, labor-saving and solvent-free, and are widely adopted in terms of depollution. However, the hot-melt adhesive is solid at room temperature, melts by heat, and solidifies by cooling to develop an adhesive force, and its adhesive force, particularly heat resistance, is limited and its use range is limited. Is the actual situation.

As hot-melt adhesives having good heat resistance, polyamide-based and polyester-based hot-melt adhesives have been developed, but these have high melting temperatures and melt viscosities, are poor in workability, and have been sufficiently put into practical use. Absent.

In recent years, so-called reactive hot melt adhesives utilizing the crosslinking reaction after bonding have been vigorously developed as means for solving the problems of conventional hot melt adhesives. A typical example of a reactive hot-melt adhesive is a reactive hot-melt adhesive whose main component is a prepolymer having an isocyanate group at the terminal end of the molecule, and which has improved heat resistance by utilizing crosslinking of the isocyanate group due to moisture after adhesion. Melt adhesives are well known. However, since the reactive hot melt adhesive has an isocyanate group, it has a problem in toxicity.

[0005]

The present invention provides a moisture-curable reactive hot-melt adhesive composition which is excellent in workability, heat resistance, adhesion to a wide range of adherends, and is less toxic. Especially.

That is, the moisture-curable reactive hot-melt adhesive composition of the present invention comprises (A) 100 parts by weight of a polymer having a hydrolyzable silicon-containing functional group, and (B) a room temperature solidifying resin 30-200. 1 part by weight and 0.1 to 20 parts by weight of the silanol condensation catalyst (C) are blended.

As the polymer having a hydrolyzable silicon-containing functional group used as the component (A) in the present invention, conventionally known polymers can be widely used, for example, JP-A-50-156.
An oxyalkylene polymer having a hydrolyzable silicon-containing functional group at the terminal end of the molecule, as proposed in JP 599, JP-A-52-73998, JP-A-62-230822, and the like. 60-228516, JP-A-6
Oxyalkylene polymers having a silicon-containing functional group and a (meth) acrylic acid (co) polymer which can be crosslinked by forming a siloxane bond as proposed in JP-A-3-112642 and JP-A-1-131127. The composition etc. which consist of coalescence can be mentioned. In particular, JP-A-60-
Oxyalkylene polymers having a silicon-containing functional group that can be crosslinked by forming a siloxane bond, as proposed in JP-A-228516, JP-A-63-112642 and JP-A-1-131127, and (meth)
A composition comprising an acrylic acid (co) polymer is preferred in terms of adhesive properties.

The component (A) of the present invention is a liquid polymer, and the present invention is characterized in that the liquid polymer is used as the main polymer of the hot melt adhesive. On the other hand, conventional hot melt adhesives have a solid polymer as a main polymer at room temperature.

The room temperature solidification-imparting resin used as the component (B) in the present invention means that the composition is solidified by mixing the component (A) which has fluidity at room temperature with heat and cooling to room temperature. It is a resin that can Examples of such room temperature solidification imparting resin include rosin and its derivatives, hydrogenated rosin, polymerized rosin, hydrogenated polymerized rosin, and (hydrogenated)
Rosing glycerin ester, (hydrogenated) rosin pentaerythritol ester, disproportionated rosing glycerin ester and hydroproportioned rosin pentaerythritol ester, (hydrogenated) terpene phenol resin, ketone resin, petroleum resin (aliphatic, aromatic, These copolymerization systems, alicyclic systems and hydrogenated petroleum resins thereof, (hydrogenated) terpene resins, coumarone / indene resins, phenol resins, xylene resins and the like are used. These room temperature solidification imparting resins may be used alone or in combination of two or more. Among the above room temperature solidifying resins, (hydrogenated) terpene phenol resin and petroleum resin are preferable in terms of workability and adhesive strength. The blending amount of the component (B) is usually 30 to 200 parts by weight, preferably 60 to 1 with respect to 100 parts by weight of the component (A).
It is 50 parts by weight. When the blending amount of the component (B) is less than 30 parts by weight, the solidification property of the obtained composition becomes insufficient,
On the other hand, when it exceeds 200 parts by weight, the melt viscosity of the resulting composition becomes high and the workability becomes poor, and the adhesiveness to a wide range of adherends, which is the object of the present invention, becomes poor.

As seen in JP-A-59-71377, an adhesive composition is known in which the resin exemplified as the component (B) in the component (A) of the present invention is blended as a tackifying resin. According to this publication, as a method of blending the component (A) and the component (B), (1) a method of dissolving the tackifying resin in an organic solvent such as toluene in advance and blending it with the component (A), (2) ) Discloses a method in which an organic solvent is added and dissolved and mixed after the component (A) and the tackifying resin are blended,
Both are compounding methods using an organic solvent. On the other hand, the composition of the present invention contains no organic solvent at all, and the composition of the present invention is obtained by heating and melting the components (A), (B) and (C) at high temperature. Has been prepared. The softening point of the composition of the present invention thus prepared is much lower than the softening point of the component (B) used, and it can be obtained from Examples described later that a pot melt adhesive composition having good workability can be obtained. it is obvious.

The silanol condensation catalyst used as the component (C) in the present invention is an essential component for condensing the hydrolyzable groups of the component (A) to promote the crosslinking of the composition of the present invention. Examples of such silanol condensation catalysts include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin laurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; dibutyltin. Reaction products of oxides and phthalates; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; lead octylate; butylamine, octylamine, Laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylene Triamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine,
2,4,6-Tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-
Amine-based compounds such as 4-methylimidazole and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), or salts of these amine compounds such as carboxylic acids; obtained from excess polyamine and polybasic acid Low molecular weight polyamide resin used; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, etc. Silanol condensation catalysts, as well as other acidic catalysts,
Well-known silanol condensation catalysts, such as a basic catalyst, are mentioned. These catalysts may be used alone or in combination of two or more. The blending amount of the component (C) is 100 parts of the component (A).
It is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on parts by weight. The blending amount of the component (C) is 0.
If it is less than 1 part by weight, the curing rate of the obtained composition will be slow and the curing reaction will not sufficiently proceed, which is not preferable. On the other hand, if it is 20 parts by weight or more, the curing rate is too fast,
It is not preferable because it deteriorates workability.

The composition of the present invention further comprises, if necessary,
Adhesiveness imparting agents such as fillers, plasticizers, silane coupling agents, waxes, antioxidants, ultraviolet absorbers, light stabilizers,
Various additives such as thixotropic agents and pigments can be appropriately added. Among these additives, it is preferable to use a silane coupling agent as an adhesion imparting agent. Especially amino groups,
A silane coupling agent having an epoxy group, a mercapto group, an isocyanate group, or a ketimine functional group is preferable in terms of adhesiveness.

[0013]

EXAMPLES The present invention will be further clarified with reference to the following examples.

Example 1 As a polymer (A) having a hydrolyzable silicon-containing functional group, Cyryl MA430 (Kanefuchi Chemical Industry Co., Ltd.) 100
0 g was placed in a 3 liter separable flask and heated so that the internal temperature was 150 ° C. Next, as a room temperature solidifying agent (B), petroleum resin FTR6100 (softening point 9
At 7 ° C, add 1000 g of Mitsui Petrochemical Co., Ltd., and add 60
Dissolved in Cyril MA430 over minutes.

After the FTR6100 was dissolved, the inside was replaced with N ₂ gas, and Stan No. which was a reaction product of dibutyltin oxide and dioctyl phthalate as a silanol condensation catalyst (C). 30 g of 918 (manufactured by Sankyo Machine Gosei Co., Ltd.) was added, and after stirring and mixing for 30 minutes, the mixture was taken out in a metal container having good airtightness and cooled to room temperature. Thus, a transparent solid composition of the present invention having a softening point of 45 ° C. was obtained.

Example 2 As in Example 1, as component (A), Cyryl MA440 was used.
YS Polystar T11, which is a terpene phenol resin as the component (B) in 1000 g (manufactured by Kanegafuchi Chemical Industry Co., Ltd.)
5 (softening point 115 ° C., manufactured by Yasuhara Yushi Co., Ltd.) was dissolved, then the inside was replaced with N ₂ gas, and Stan NO. 918 (manufactured by Sankyo Machine Gosei Co., Ltd.) and a silane coupling agent (KBM40) which is an adhesiveness-imparting agent.
3, g-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (30 g) was added, thoroughly mixed and dispersed, taken out in a metal container having good airtightness, and cooled to room temperature. Thus, a transparent solid composition of the present invention having a softening point of 50 ° C. was obtained.

The moisture-curable reactive hot-melt adhesive composition prepared in this manner, a commercially available reactive hot-melt adhesive utilizing crosslinking of isocyanate groups, Bond MR2021 (manufactured by Konishi Co., Ltd., Comparative Example 1) And MH- which is a commercially available EVA hot melt adhesive.
A performance comparison test of 193 (manufactured by Konishi Co., Ltd., referred to as Comparative Example 2) was performed by the following method.

[0018] Each of the compositions of meltable Examples 1-2 and Comparative Examples 1-2, about 10g weighed to the glass container was sealed and left in an oven, 3
The temperature was raised from 0 ° C. at a rate of 1 ° C./min, the temperature at which the sample was completely melted was measured, and the meltability was judged according to the following criteria.

⊚: 80 ° C. or lower, ◯: 80 to 100 ° C.,
Δ: 100 to 150 ° C., ×: 150 ° C. or higher.

An adherend is a birch cherry tree having an adhesive force of 25 mm × 100 mm × 5 mm. The compositions of Examples 1-2 are 80 ° C., Comparative Examples 1-2
The composition of 1 is heated and melted at 170 ° C., applied to one of the adherends so that the adhesive area is 25 mm × 25 mm, the other adherend is immediately adhered, and a weight of 1 kg is put on for 30 seconds and pressed. Tighten. Further, it is aged at 20 ° C. and 60% RH for 7 days, and the tensile shear strength is measured. Normal adhesive strength is 2 after curing
Measure at 0 ° C. The heat resistant adhesive strength is measured after curing at 80 ° C. for 2 hours and at a temperature of 80 ° C.

Adhesiveness The compositions of Examples 1 and 2 were heated and melted at 80 ° C., and the compositions of Comparative Examples 1 and 2 were heated and melted at 170 ° C., and applied to the adherend in a bead form at 20 ° C. and 60% RH. After curing for 7 days, a cut was made at one interface between the adhesive and the adherend with a cutter knife, and the adhesive was manually peeled off at an angle of 90 ° to the adherend, and the adhesiveness was judged according to the following criteria.

∘: Cohesive failure of adhesive, Δ: Cohesive failure of adhesive, mixed failure of interface failure, ×: Interface failure. Results are shown in Tables 1 and 2.

[0023]

[Table 1]

[0024]

[Table 2]

Claims (1)

[Claims] 1. (A) 100 parts by weight of a polymer having a hydrolyzable silicon-containing functional group, (B) a room temperature solidifying resin 30-
200 parts by weight and (C) silanol condensation catalyst 0.1-2
A moisture-curable reactive hot melt adhesive composition comprising 0 part by weight.