JPH05112766A - Solvent-based two-pack adhesive and base thereof - Google Patents

Abstract

PURPOSE:To obtain the title adhesive which can exhibit excellent adhesiveness in bonding a composite member such as a member made of an olefin-resin- impregnated wood fiber by using a base comprising a specified polyurethane compound and a curing agent comprising a specified compound. CONSTITUTION:The title adhesive comprises a base comprising a hydroxy- terminated polyurethane compound obtained by reacting a polyol (e.g. ethylene glycol) with a polyurethane reaction product terminated with an active isocyanate group and obtained by reacting a saturated polyester polyol (e.g. polyhexamethylene adipate polyol) with a hydrophilic component containing a hydrophilic group and at least two NCO-reactive functional groups (e.g. 2,2- dimethylolpropionic acid) and a diisocyanate compound (e.g. hexamethylene diisocyanate) and a curing agent comprising a polyisocyanate compound (e.g. triphenylmethane triisocyanate).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent-based two-component type adhesive in which two liquids (a main agent and a curing agent) are mixed immediately before use. In particular, wood fibers such as hemp pulp are mixed with polypropylene (PP). ), A urethane-based solvent-based two-part liquid exhibiting a large initial adhesive force and normal adhesive force in bonding a member formed by binding with a polyolefin resin such as polyethylene (PE) to a soft vinyl chloride resin sheet Mold adhesive.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
For example, a solvent-based adhesive such as polyester polyurethane rubber has been used for bonding a soft vinyl chloride resin sheet and a substrate made of an olefin resin-impregnated wood fiber, but sufficient bonding performance has not been obtained.

Then, as a result of earnest studies, the inventors of the present invention improved the affinity of the adhesive with respect to the wood fiber containing a large amount of hydrophilic groups contained in the base material, and as a result, the adhesive and the base material. It was found that the adhesiveness with

The present invention has been made on the basis of such findings, and its object is to adhere the adherend with a conventional solvent-based adhesive such as an olefin resin-impregnated wood fiber member. It is an object of the present invention to provide a solvent-based two-component type adhesive that exhibits excellent adhesive force even when the composite member is insufficient.

[0005]

[Means for Solving the Problems] A solvent-based two-pack type adhesive according to the present invention for achieving the above object is a saturated polyester polyol (1), at least two hydrophilic groups and a group capable of reacting with an isocyanate group. By reacting a hydrophilic component (2) having a functional group of 1) and a diisocyanate compound (3) with a polyurethane-based reaction product having an active isocyanate group at the molecular end, and a polyol (4). It is composed of a main agent containing a polyurethane compound (A) having a hydroxyl group at the obtained molecular end and a polyisocyanate compound (B) as a curing agent.

The saturated polyester polyol (1) in the present invention can be used without particular limitation, and examples thereof include terephthalic acid type polyesters such as polyethylene terephthalate and polytetramethylene terephthalate, polyethylene isophthalate and polytetramethylene isophthalate. Aromatic polyesters such as isophthalic acid type polyesters; polyethylene oxalate, polytrimethylene oxalate, polytetramethylene oxalate, polyhexamethylene oxalate, polyoctamethylene oxalate, polydecamethylene oxalate,
Polyicosamethylene oxalate, polyicosamethylene malonate, polyethylene succinate, polytetramethylene succinate, polyhexamethylene succinate, polydecamethylene succinate, poly icosamethylene succinate, polydecamethylene glutarate , Polyicosamethylene glutarate, polytetramethylene adipate, polyhexamethylene adipate, polydecamethylene adipate, polyicosamethylene adipate, polyhexamethylene pimelate, polydecamethylene pimelate, polyicosamethylene pimelate, polyethylene subbe Rate, polyhexamethylene suberate, polydecamethylene suberate, polyicosamethylene suberate, polyhexamethylene azelate, polydecamethylene azelate, polyethylene se Sebacate, polytetramethylene sebacate, poly pentamethylene sebacate, polyhexamethylene sebacate, polydecamethylene sebacate, linear aliphatic polyesters, such as poly equalizing support sebacate and the like. The preferred molecular weight of the saturated polyester polyol (1) is 1,000 to 5,000.

The hydrophilic component (2) in the present invention has at least two functional groups capable of reacting with an isocyanate group at the terminal or side chain, and imparts hydrophilicity to the resulting polyurethane compound. COOH, -COONa,
_{-COONH 4, -SO 3 H, -SO} 3 Na, -SO 3
It has at least one hydrophilic group such as NH ₄ in the molecule. Specific examples of the hydrophilic component (2) include:
In addition to 2,2-dimethylolpropionic acid (DMPA),
Sulfonic acid-based compounds represented by the following chemical formulas 1 and 2, chemical formulas 3 and 4,
Anionic hydrophilicity imparting substances such as carboxylic acid type shown in Chemical formula 5 and cationic hydrophilicity imparting substances shown in Chemical formulas 6 and 7 below can be mentioned.

[0008]

[Chemical 1]

[0009]

[Chemical 2]

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

The diisocyanate compound (3) in the present invention is reacted with the above-mentioned two components, that is, the saturated polyester polyol (1) and the hydrophilic component (2),
In addition, it is used to obtain a polyurethane-based reaction product having isocyanate groups at both ends. Examples of the diisocyanate compound (3) include hexamethylene diisocyanate (HDI), diphenylmethane-4,4′-diisocyanate (MDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPD).
I), aliphatic or aromatic diisocyanates such as m-xylylene diisocyanate (XDI), and hydrogenated compounds thereof.

The polyol (4) in the present invention can convert the isocyanate group at the end of the polyurethane reaction product into a hydroxyl group and can be crosslinked and cured by a curing agent (polyisocyanate compound (B)) via a urethane bond. It is for Preferable specific examples of the polyol (4) include low molecular weight compounds such as ethylene glycol, propylene glycol, hexanediol, ethanolamine and butanediol. The preferred blending ratio of the saturated polyester polyol (1), the hydrophilic component (2), the diisocyanate compound (3), and the polyol (4) in the present invention is hydrophilic with respect to nmole of the saturated polyester polyol (1). Ingredient (2) n ±
1 mol, diisocyanate compound (3) 2n + 2 mol,
It is 2 mol of polyol (4). The preferred molecular weight of the polyurethane compound (A) is 5,000 to 100,0.
00, more preferably 10,000 to 50,000.

Examples of the polyisocyanate compound (B) as the solvent-based curing agent in the present invention include the compounds listed as the specific examples of the diisocyanate compound (3) and derivatives thereof. In addition, HDI derivatives such as HDI trimethylolpropane (TMP) adduct trimer and isocyanurate trimer, MDI TMP adduct trimer, crude MDI and other MDI derivatives, TDI TMP
TDI derivative such as adduct trimer or isocyanurate trimer, IPDI derivative such as IPDI TMP adduct trimer or isocyanurate trimer, XDI derivative such as XDI TMP adduct trimer or isocyanurate trimer ,
It is also possible to use tris (p-isocyanatephenyl) thiophosphate and trisphenylmethane triisocyanate (trade name "Desmodur R" manufactured by Bayer). A suitable mixing ratio of the main agent and the curing agent in the present invention is isocyanate group / hydroxyl group (NCO / OH)
In terms of conversion, the range of 1 to 10 is suitable.

As described above, the main component of the solvent-based two-component adhesive according to the present invention contains in its molecule a polyester polyol component having a large cohesive force and a hydrophilic component having a large affinity for the hydrophilic component-containing member. It will be. Therefore, the adhesive according to the present invention containing this as a main component is particularly suitable for use in bonding hydrophilic component-containing members such as olefin resin-impregnated wood fiber members. Incidentally, in order to improve the initial cohesive force, a polyester polyurethane rubber which has been widely used for solvent adhesives in the past may be blended. The preferred blending amount of this polyester polyurethane rubber is 0 per 100 parts by weight of the polyurethane compound.
~ 500 parts by weight.

The main component of the solvent-based two-component adhesive according to the present invention is produced, for example, by the steps described below. [Step] Saturated polyester polyol (1)
It is dissolved in an organic solvent such as acetone, methyl ethyl ketone (MEK), xylene and toluene in a reactor equipped with a heating means and a reflux device. [Step] The hydrophilic component (2) is added to the organic solution obtained in the step, and the temperature is maintained at 40 to 100 ° C. [Step] The diisocyanate compound (3) is added to the liquid obtained in the step, and a binding reaction is carried out for 2 to 12 hours while stirring to obtain a polyurethane-based reaction product having an active isocyanate group at a molecular end. If necessary, catalysts such as amines and organotin compounds may be added. [Step] The polyol (4) is added to the melt of the polyurethane reaction product obtained in the step, and the addition reaction is carried out while stirring for 2 to 12 hours to convert the terminal isocyanate group of the polyurethane reaction product into a hydroxyl group to produce a polyurethane. A main agent consisting of the compound (A) is obtained.

The method for producing the main agent in the present invention described above is merely an example, and it goes without saying that it is not intended to exclude those produced by methods other than the above-described method. When the main agent obtained as described above is mixed with a curing agent by stirring to be used as an adhesive, and the adhesive is applied to an adherend and cured at room temperature or by heat, strong adhesion is realized.

[0021]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.

(1) Preparation of Main Agent Synthesis of Polyurethane Compound (A) -1 Polyhexamethylene adipate polyol (average molecular weight Mw: about 2000) was dissolved in toluene in a reactor equipped with a heating means and a reflux device. Then, 2,2-dimethylolpropionic acid was further charged, and the temperature was maintained at 80 ° C. Next, after adding HDI and reacting for 10 hours, ethylene glycol was further added and reacted for 10 hours to obtain polyurethane compound (A) -1. Synthesis of Polyurethane Compound (A) -2 Polyurethane compound (A) -2 was obtained in the same manner as in (1) above except that 2,2-dimethylolpropionic acid was not added. However, NCO / OH is the above (1)
Was synthesized by reacting so that the same ratio was obtained. Table 1 shows the amount (unit: gram) of each raw material used in (1) and above.

[0023]

[Table 1]

(2) Examples 1 to 4 and Comparative Examples 1 to 3 (Example 1) 100 g of polyester polyurethane rubber (manufactured by Bayer, product code "Desmocoll 500") and a polyurethane compound ((A) -1) ) 50 g was dissolved in 850 g of acetone while stirring and mixing to prepare a main agent. Next, to 1000 g of this main agent, 50 g of Desmodur R (trisphenylmethanetriisocyanate) as a curing agent was added and mixed with stirring to prepare an adhesive. (Example 2) Example 1 was repeated except that the same amount of polyester polyurethane rubber (manufactured by Bayer, product code "Desmocoll 530") was used instead of Desmocoll 500.
An adhesive was prepared in the same manner as in. Example 3 Example 1 was repeated except that the same amount of polyester polyurethane rubber (manufactured by Bayer Co., Ltd., product code “Desmocoll 540”) was used instead of Desmocoll 500.
An adhesive was prepared in the same manner as in. (Example 4) 50 g of a polyurethane compound ((A) -1) was dissolved in 150 g of acetone to prepare a main agent.
Then, 10 g of Desmodur R as a curing agent was added to 200 g of this base material and mixed by stirring to prepare an adhesive. (Comparative Example 1) An adhesive was prepared in the same manner as in Example 1 except that the same amount of the polyurethane compound (A) -2 was used instead of the polyurethane compound (A) -1. (Comparative Example 2) An adhesive was prepared in the same manner as in Example 2 except that the same amount of the polyurethane compound (A) -2 was used instead of the polyurethane compound (A) -1. (Comparative Example 3) An adhesive was prepared in the same manner as in Example 3 except that the same amount of the polyurethane compound (A) -2 was used instead of the polyurethane compound (A) -1. Table 2
The amount of each component used in Examples 1 to 4 and Comparative Examples 1 to 3 (unit: gram) is collectively shown in.

[0025]

[Table 2]

(3) Adhesive Strength Evaluation Test The initial adhesive strength and normal adhesive strength of each adhesive were measured by the following test methods. That is, each adhesive was spray-applied to a base material (PP resin-impregnated wood fiber board, 100 × 100 mm size) at an application amount of 150 g / m ² , and then ² at 80 ° C.
Dry for minutes. On the side of the spray-coated surface of this substrate, 140
Skin material heated at 4 ° C for 4 minutes (soft vinyl chloride resin board manufactured by Sunstar Giken Co., Ltd., trade name “Orcia MP6
77 ", 100 x 100 mm size)
Clamping was performed for 10 seconds with a pressure of 0.5 Kg / cm ² to obtain Samples 1 to 4 and Comparative Samples 1 to 3. Next, each sample was cut into a width of 25 mm to obtain four test pieces, each of which was peeled by 10 mm in the longitudinal direction, then mounted on a tensile tester, and peeled by 180 ° at a speed of 200 mm / min to peel strength ( (Kg / 25 mm) was calculated, and the average of four test pieces was calculated as the adhesive strength. The results are shown in Table 3.

In Table 3, the initial adhesive strength is 1 at room temperature after pressure bonding.
The measurement result after leaving for 0 minutes is shown.
The results of measurement after leaving for 1 day at room temperature after pressure bonding are shown. In the same table, MB indicates that the skin material was destroyed (Mate
rial break), CF indicates that the adhesive layer has broken (Cohesive Failure), and AF indicates that it has broken at the interface between the substrate and the adhesive layer (Adhesive Failur).
e).

[0028]

[Table 3]

From Table 3, the adhesives (Samples 1 to 4) according to the present invention in which the polyurethane compound (A) -1 containing the hydrophilic component was blended, aggregated at the time of applying a certain load in the initial stage of the adhesion. Although the material breaks, the material is destroyed after the normal state, and it can be seen that the adhesive strength is high. On the other hand, an adhesive containing a polyurethane compound (A) -2 containing no hydrophilic component (Comparative Sample 1
In 3 and 3), both at the initial stage of adhesion and after normal state, the interface peeled off at the time of light load, and it can be seen that the adhesive force is small.

[0030]

As described above in detail, the solvent-based two-component type adhesive agent according to the present invention is an olefin resin-impregnated wood fiber member, etc., which was not sufficiently adhered by the conventional solvent type adhesive agent. The present invention exerts an excellent and unique effect such as bonding the composite member of (1) with a large adhesive force.

Claims (4)

[Claims] 1. A saturated polyester polyol (1), a hydrophilic component (2) having a hydrophilic group and at least two functional groups capable of reacting with an isocyanate group, and a diisocyanate compound (3) are reacted. A main agent containing a polyurethane compound (A) having a hydroxyl group at the molecular end obtained by reacting the obtained polyurethane-based reaction product having an active isocyanate group at the molecular end with a polyol (4), and a poly (C) as a curing agent. A solvent-based two-component adhesive comprising an isocyanate compound (B). 2. The solvent-based two-component adhesive according to claim 1, wherein the main component contains polyester polyurethane rubber. 3. The solvent-based two-component adhesive according to claim 1, wherein at least one of the adherends is a hydrophilic component-containing member. 4. A saturated polyester polyol (1), a hydrophilic group (2) having a hydrophilic group and at least two functional groups capable of reacting with an isocyanate group, and a diisocyanate compound (3) are reacted. For a solvent-based two-component adhesive containing a polyurethane compound (A) having a hydroxyl group at the molecular end obtained by reacting the resulting polyurethane-based reaction product having an active isocyanate group at the molecular end with a polyol (4) Main agent.