JP2014058629A - Adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive including a plant-derived epoxidized soybean oil as a main raw material.SOLUTION: An epoxidized soybean oil and a polypropylene glycol with amino groups at both ends are blended so that the equivalent ratio of the epoxy groups of the epoxidized soybean oil to the active hydrogen groups of the polypropylene glycol with amino groups at both ends becomes 1:1.2 to 1:1.6. Alternatively, an epoxidized soybean oil, a polypropylene glycol with amino groups at both ends, and 4,4'-diaminodiphenylmethane are blended so that the equivalent ratio of the epoxy groups of the epoxidized soybean oil to the active hydrogen groups of the polypropylene glycol with amino groups at both ends to the active hydrogen groups of the 4,4'-diaminodiphenylmethane becomes 1:1:0.2 to 1:1:0.4.

Description

  The present invention relates to an adhesive.

  Adhesives are used in a wide range of fields such as adhesive tapes, protective films, and semiconductor processes, and rubbers, acrylic resins, and silicones are often used as base resins. Most of these resins are petroleum-derived resins except for natural rubber.

  In recent years, interest in plant-derived pressure-sensitive adhesives has increased due to an increase in natural orientation. For example, Patent Document 1 discloses a pressure-sensitive adhesive mainly composed of epoxidized natural fats and oils, specifically epoxidized soybean oil. Has been proposed.

WO2012 / 024301 A1

  Patent Document 1 describes a combination of epoxidized soybean oil and diamine as a pressure-sensitive adhesive mainly composed of epoxidized soybean oil. As a result of studies by the inventors, specific examples of the diamine are described. It has been found that a curing agent having a relatively short molecular chain such as hexamethylenediamine described as No. 1 is hard rubber and does not exhibit adhesiveness and is difficult to use as an adhesive.

  This invention is made | formed in view of the above points, Comprising: It aims at providing the adhesive which uses a plant-derived epoxidized soybean oil as a main raw material.

  In order to achieve the above object, the present invention is configured as follows.

  The pressure-sensitive adhesive according to the first aspect of the present invention comprises an epoxidized soybean oil and a polypropylene glycol both-end amine, and the epoxidized soybean oil and the polypropylene glycol both-end amine are combined with an epoxy group of the epoxidized soybean oil. It mix | blends so that it may become 1: 1.2-1: 1.6 by the equivalent ratio with the active hydrogen group of the said polypropylene glycol both terminal amine.

  The pressure-sensitive adhesive according to the second invention of the present invention comprises epoxidized soybean oil, polypropylene glycol both-end amine, and 4,4′-diaminodiphenylmethane, and the epoxidized soybean oil, the polypropylene glycol both-end amine, and the above 4,4′-diaminodiphenylmethane is 1: 1 with an equivalent ratio of the epoxy group of the epoxidized soybean oil, the active hydrogen group of the amine at both ends of the polypropylene glycol and the active hydrogen group of the 4,4′-diaminodiphenylmethane. : It mix | blends so that it may become 0.2-1: 1: 0.4.

  In a preferred embodiment, the polypropylene glycol both terminal amines have an average molecular weight of 400.

  According to the present invention, adhesiveness can be expressed by blending polypropylene glycol both terminal amines not disclosed in Patent Document 1 as a curing agent for epoxidized soybean oil. An adhesive having epoxidized soybean oil as a main raw material can be obtained.

  According to the present invention, adhesiveness can be expressed by blending polypropylene glycol both terminal amines not disclosed in Patent Document 1 in a specific ratio as a curing agent for epoxidized soybean oil. It is possible to obtain a pressure-sensitive adhesive using epoxidized soybean oil as a main raw material.

  Hereinafter, the adhesive according to the embodiment of the present invention will be described in detail.

  The pressure-sensitive adhesive according to the first invention of the present invention includes epoxidized soybean oil and polypropylene glycol both terminal amines.

  Epoxy soybean oil (ESO) having a conventionally known composition can be used. Examples of commercially available oils include Kapox S-6 (trade name) manufactured by Kao Corporation and NOF Corporation. New Sizer 510R (trade name) manufactured by Co., Ltd. can be used.

  The chemical structural formula of epoxidized soybean oil can be represented by the following formula (1).

  Epoxidized soybean oil contains, for example, linoleic acid 54% (2), oleic acid 23% (1), palmitic acid 11% (0), linolenic acid 7% (2), stearic acid 4% (0) When the numerical value in the parentheses is the number of epoxy groups, the number of epoxy groups in the epoxidized soybean oil is 4.35.

  Polypropylene glycol both-end amine as a curing agent is a polypropylene glycol (PPG: polypropyleneglycol) having a low glass transition temperature (Tg) and an amino group bonded to both ends of the molecule, and is a diamine having a propylene skeleton (polyoxyalkylene diamine). is there.

  The chemical structural formula of this polypropylene glycol both terminal amine can be shown by the following formula (2).

  The average molecular weight of the polypropylene glycol both terminal amines is 200-2000, preferably about 400.

  As the polypropylene glycol both terminal amines, those having a conventionally known composition are used, and examples of commercially available ones include ether amine D400 manufactured by Mitsui Chemicals Fine Co., Ltd.

  The pressure-sensitive adhesive according to the first aspect of the present invention comprises an epoxidized soybean oil and a polypropylene glycol terminal amine at an equivalent ratio of an epoxy group of the epoxidized soybean oil and an active hydrogen group of both ends of the polypropylene glycol amine 1: It mix | blends so that it may be set to 1.2 to 1: 1.6, Preferably it is 1: 1.3 to 1: 1.5.

  When the equivalent ratio of the active hydrogen groups of the amines at both ends of polypropylene glycol to the epoxy groups of epoxidized soybean oil is less than 1.2 or more than 1.6, it exhibits fluidity at room temperature and has a sticky chickenpox shape. This is not preferable because the adhesive strength is lowered.

  Thus, when the equivalent ratio of the active hydrogen groups of both end amines of polypropylene glycol to the epoxy groups of the epoxidized soybean oil is less than 1.2 or more than 1.6, the reason why it becomes sticky chickenpox is as follows: If it is less than 1.2, the curing agent is insufficient and does not cure sufficiently. Conversely, if it exceeds 1.6, it is considered that the excess of the curing agent works as a plasticizer.

  However, the adhesive according to the second invention of the present invention, even when the equivalent ratio of the active hydrogen groups of both ends of the polypropylene glycol to the epoxy group of the epoxidized soybean oil is less than the equivalent ratio defined in the first invention of 1.2. The agent exhibits good tackiness without exhibiting fluidity at room temperature.

  The pressure-sensitive adhesive according to the second invention of the present invention contains 4,4′-diaminodiphenylmethane (DDM), which is an aromatic diamine, in addition to the above-mentioned epoxidized soybean oil and polypropylene glycol both terminal amines. .

  The chemical structural formula of 4,4-'diaminodiphenylmethane is represented by the following formula (3).

  The pressure-sensitive adhesive according to the second invention comprises an epoxidized soybean oil, a polypropylene glycol both terminal amine, and 4,4′-diaminodiphenylmethane, an epoxy group of the epoxidized soybean oil, and an active hydrogen group of the polypropylene glycol both terminal amine. Preferably, 1: 1: 0.3-1: 0.4 so that the equivalent ratio of the 4,4'-diaminodiphenylmethane to the active hydrogen group is 1: 1: 0.2-1: 1: 0.4. It mix | blends so that it may become 1: 0.4.

  When the equivalent ratio of the active hydrogen groups of 4,4′-diaminodiphenylmethane to the epoxy groups of the epoxidized soybean oil is less than 0.2, tackiness is not recognized. It does not dissolve and is not preferred.

  The pressure-sensitive adhesive of the present invention includes, for example, softeners, anti-aging agents, fillers, ultraviolet absorbers, light stabilizers, tackifiers, in addition to epoxidized soybean oil, polypropylene glycol both terminal amines, and 4,4′-diaminodiphenylmethane. Various additives such as fire (tackifier) may be appropriately selected and added.

[Example]
Next, the present invention will be described in more detail based on specific examples and comparative examples, but the present invention is not limited to these examples.

  Table 1 below shows epoxidized soybean oil (ESO) used in Examples and Comparative Examples, polypropylene glycol both terminal amines (D400) having an average molecular weight of 400, and molecular weights of 4,4′-diaminodiphenylmethane (DDM) (g / Mol), the number of reaction points (pieces), and equivalent (g / eq.).

  Sample No. 1 was prepared by blending the epoxidized soybean oil (ESO) in Table 1 and the polypropylene glycol both terminal amines (D400) having an average molecular weight of 400 so as to have an equivalent ratio in Table 2 below. 1-4 adhesives were prepared and their properties were evaluated.

  As the epoxidized soybean oil (ESO), Kapox S-6 (trade name) manufactured by Kao Corporation is used, and as the polypropylene glycol both terminal amine (D400) having an average molecular weight of 400, ether manufactured by Mitsui Chemical Fine Co., Ltd. Amine D400 was used.

  A method for producing the adhesive for each sample will be described.

  As shown in Table 1 above, the epoxy group equivalent of epoxidized soybean oil (ESO) is 214 (g / eq.), And the active hydrogen groups of the polypropylene glycol both terminal amines (D400) having an average molecular weight of 400 are as follows. Since the equivalent is 100 (g / eq.), Sample No. 1 with an equivalent ratio of 1: 1 is used. 1, the weight ratio of the epoxidized soybean oil (ESO) and the polypropylene glycol both terminal amine (D400) having an average molecular weight of 400 is 214 (g): 100 (g).

  Similarly, sample no. 2, the weight ratio of epoxidized soybean oil (ESO) to polypropylene glycol both terminal amine (D400) was 214 (g): 130 (g), and the equivalent ratio was 1: 1.5. 3, the weight ratio of epoxidized soybean oil (ESO) and polypropylene glycol both terminal amine (D400) was 214 (g): 150 (g), and the equivalent ratio was 1: 1.7. In No. 4, the weight ratio of epoxidized soybean oil (ESO) and polypropylene glycol both terminal amine (D400) is 214 (g): 170 (g).

  Epoxidized soybean oil (ESO) and polypropylene glycol both terminal amines (D400) were blended so as to have the above weight ratios, stirred by hand for 2 minutes, and then left at 120 ° C. for 7 days in a thermostatic bath. Then, reaction hardening was carried out. 1-4 adhesives were produced.

  After reaction curing, the viscosity is high, so it was dissolved in ethyl acetate as a solvent for coating, coated on a PET (polyethylene terephthalate) substrate using an applicator, and a surface paper was bonded to prepare a tack paper .

  Each sample No. created as described above was used. Each characteristic shown in the said Table 2 was evaluated about the adhesive of 1-4 and tack paper.

  Specifically, regarding the fluidity at room temperature, the prepared adhesive was placed in a beaker, and the presence or absence of the fluidity of the adhesive when the beaker was tilted was visually evaluated.

  The tack was evaluated by touching the adhesive in a beaker with a finger.

  About hot melt (HM) coating, it heated at 150 degreeC and evaluated the coating property of the adhesive.

  About solvent solubility, the solubility of the adhesive with respect to ethyl acetate was evaluated.

The coating amount (g / mm ² ) was calculated by diluting to 20% with ethyl acetate, coating the PET substrate with a thickness of 100 μm with a small applicator, and measuring the weight after drying.

  The adhesive force was measured by attaching the tack paper of each sample to stainless steel (SUS) and polyethylene (PE), respectively, and measuring the force required to peel it off in the 180 degree direction according to JIS Z 0237.

  Table 2 above defines the equivalent ratio of the epoxy groups of epoxidized soybean oil (ESO) and the active hydrogen groups of both end amines of polypropylene glycol (D400) in the range of 1: 1.2 to 1: 1.6. The Example and comparative example of an adhesive which concern on 1st invention are shown.

  Sample No. In Comparative Example 1 of 1, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO) and the active hydrogen group of both end amines of polypropylene glycol (D400) is 1: 1, and the equivalent ratio defined in the first invention is 1 : Out of the range of 1.2 to 1: 1.6. As shown in Table 2, this Comparative Example 1 exhibits fluidity at room temperature, has a high viscosity, has a sticky string-like tack, and cannot be used as an adhesive. The properties were not evaluated.

  Sample No. In Comparative Example 2 of No. 4, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO) and the active hydrogen group of both end amines of polypropylene glycol (D400) is 1: 1.7, and the equivalent amount defined in the first invention The ratio is outside the range of 1: 1.2 to 1: 1.6. As shown in Table 2, this Comparative Example 2 exhibits fluidity at room temperature, has a high viscosity, and is hard, but has a sticky string-like tack, and can be used as an adhesive. It was not possible to evaluate other characteristics.

  In contrast, sample no. In Example 1 of No. 2, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO) and the active hydrogen group of both end amines of polypropylene glycol (D400) is 1: 1.3, and the equivalent amount defined in the first invention The ratio is in the range of 1: 1.2 to 1: 1.6. In Example 1, as shown in Table 2, there was no fluidity at room temperature, and moderate tack was recognized. Moreover, although it could not be coated even when heated to 150 ° C., it showed good solubility in ethyl acetate as a solvent. Furthermore, the adhesive force was shown with respect to both stainless steel (SUS) and polyethylene (PE).

  Sample No. In Example 2 of No. 3, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO) and the active hydrogen group of both end amines of polypropylene glycol (D400) was 1: 1.5, and the equivalent amount defined in the first invention The ratio is in the range of 1: 1.2 to 1: 1.6. In Example 2, as shown in Table 2, there was no fluidity at room temperature and it was hard but moderate tack was recognized. Further, although it could not be applied even when heated to 150 ° C., it was slightly gelled but soluble in ethyl acetate as a solvent. Furthermore, the adhesive strength stronger than Example 1 was shown with respect to both stainless steel (SUS) and polyethylene (PE).

  Thus, an example in which the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO) and the active hydrogen group of both end amines of polypropylene glycol (D400) is in the range of 1: 1.2 to 1: 1.6. It can be seen that Nos. 1 and 2 show good characteristics and can be used as pressure-sensitive adhesives.

  The epoxidized soybean oil (ESO) of Table 1, polypropylene glycol both-end amine (D400) having an average molecular weight of 400, and 4,4′-diaminodiphenylmethane (DDM) were blended so as to have an equivalent ratio of Table 3 below. Sample No. The adhesives of 5-7 were produced similarly to the sample of above-mentioned Table 2, and the characteristic was evaluated similarly.

  This Table 3 shows the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO), the active hydrogen group of both end amines of polypropylene glycol (D400), and the active hydrogen group of 4,4′-diaminodiphenylmethane to 1: 1: 0. Examples and comparative examples of the pressure-sensitive adhesive according to the second invention specified in the range of 2 to 1: 1: 0.4 are shown.

  Sample No. In Comparative Example 3 of No. 6, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO), the active hydrogen group of both ends amine of polypropylene glycol (D400) and the active hydrogen group of 4,4′-diaminodiphenylmethane is 1: 1. : 0.5, which is outside the range of equivalent ratio 1: 1: 0.2 to 1: 1: 0.4 defined in the second invention. In Comparative Example 3, as shown in Table 3, there was no fluidity at room temperature, and it was hard but moderate tack was recognized. However, even when heated to 150 ° C., coating was not possible, it did not dissolve in ethyl acetate as a solvent, became a gel, and could not be used as an adhesive, and other properties were not evaluated.

  Sample No. In Comparative Example 4 of No. 7, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO), the active hydrogen group of both ends amine of polypropylene glycol (D400) and the active hydrogen group of 4,4′-diaminodiphenylmethane was 1: 0. .8: 0.7, which is outside the range of equivalent ratio 1: 1: 0.2 to 1: 1: 0.4 specified in the second invention. As shown in Table 3, Comparative Example 4 was not fluid at room temperature, but had no tack, was rubbery, could not be used as an adhesive, and other properties were not evaluated. It was.

  In contrast, sample no. Example 3 of No. 5 has an equivalence ratio of 1: 1 between the epoxy group of epoxidized soybean oil (ESO), the active hydrogen group of both ends amine of polypropylene glycol (D400) and the active hydrogen group of 4,4′-diaminodiphenylmethane. : 0.3, and the equivalent ratio defined in the second invention is within the range of 1: 1: 0.2 to 1: 1: 0.4. In Example 3, as shown in Table 3, there was no fluidity at room temperature, and moderate tack was recognized. Further, although it could not be applied even when heated to 150 ° C., it was slightly gelled but soluble in ethyl acetate as a solvent. Furthermore, the adhesive force was shown with respect to both stainless steel (SUS) and polyethylene (PE).

  Thus, the equivalent ratio of the epoxy group of epoxidized soybean oil (ESO), the active hydrogen group of both ends amine of polypropylene glycol (D400), and the active hydrogen group of 4,4′-diaminodiphenylmethane is 1: 1: 0. It turns out that Example 3 which exists in the range of 2: 1: 1: 0.4 shows a favorable characteristic, and can be used as an adhesive.

  As described above, by blending the polypropylene glycol both terminal amines not disclosed in Patent Document 1 at a specific ratio as a curing agent for epoxidized soybean oil, it is possible to develop adhesiveness, and plant-derived epoxy It is possible to obtain a pressure-sensitive adhesive mainly using modified soybean oil.

Claims (4)

Epoxidized soybean oil and polypropylene glycol both terminal amines,
The epoxidized soybean oil and the polypropylene glycol both-end amine are used in an equivalent ratio of 1: 1.2 to 1: 1.6 of the epoxy group of the epoxidized soybean oil and the active hydrogen group of the both-end amine of the polypropylene glycol. Formulate so that
A pressure-sensitive adhesive. The average molecular weight of the polypropylene glycol both terminal amines is 400.
The pressure-sensitive adhesive according to claim 1. Including epoxidized soybean oil, polypropylene glycol both terminal amine and 4,4-diaminodiphenylmethane,
The epoxidized soybean oil, the amine of both ends of the polypropylene glycol and the 4,4-diaminodiphenylmethane, the epoxy group of the epoxidized soybean oil, the active hydrogen group of the amine of both ends of the polypropylene glycol and the 4,4-diaminodiphenylmethane. So as to have an equivalent ratio of 1: 1: 0.2 to 1: 1: 0.4 with an active hydrogen group of
A pressure-sensitive adhesive. The average molecular weight of the polypropylene glycol both terminal amines is 400.
The pressure-sensitive adhesive according to claim 3.