KR101775759B1 - Adhesive composition with excellent durability - Google Patents
Adhesive composition with excellent durability Download PDFInfo
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- KR101775759B1 KR101775759B1 KR1020140049735A KR20140049735A KR101775759B1 KR 101775759 B1 KR101775759 B1 KR 101775759B1 KR 1020140049735 A KR1020140049735 A KR 1020140049735A KR 20140049735 A KR20140049735 A KR 20140049735A KR 101775759 B1 KR101775759 B1 KR 101775759B1
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Abstract
The present invention relates to a rubber-based resin; A first curing agent; And a second curing agent, wherein the second curing agent is a thiol compound.
Description
The present invention relates to a rubber-based pressure-sensitive adhesive composition having excellent durability.
It is well known in the art that touch materials, including various packaged electronic devices or transparent conductive films, require moisture protection to maintain excellent operation or a constant shelf life. Furthermore, much attention has recently been focused on the development of pressure-sensitive adhesive compositions for increasing the durability of next generation devices such as OLEDs or touch screens.
Of the various pressure-sensitive adhesive compositions, only the invention for the acrylic pressure-sensitive adhesive composition is continued, and the rubber-based pressure-sensitive adhesive composition has poor durability due to multiple bonds and is not used as a pressure-sensitive adhesive composition. Therefore, there is a need for research to improve the durability of the rubber-based pressure-sensitive adhesive composition.
The present invention relates to a rubber-based resin; A first curing agent; And a second curing agent, wherein the second curing agent is a thiol compound, and the like.
However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.
The present invention relates to a rubber-based resin; A first curing agent; And a second curing agent, wherein the second curing agent is a thiol compound.
The rubber-based resin may be at least one selected from the group consisting of styrene-butadiene-styrene (SBS) rubber, styrene-butadiene (SB) rubber, styrene-isoprene-styrene (SIS) rubber, styrene- Rubber (LATEX), and butyl rubber.
The first curing agent may be selected from the group consisting of 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, tetramethylol Tetramethylol methane triacrylate, trimethylolpropane triacrylate, 1,6-bis (3-acryloyloxy) -2-hydroxypropyloxy) hexane [ -2-hydroxypropyl) hexane, polyethylene glycol diacrylate, pentaerythritol triacrylate, and hexamethylene diisocyanate urethane prepolymer. It can be more than one.
The thiol compound may be a compound having two or more primary thiol groups in the molecule.
The rubber-based resin may be 50 to 80 parts by weight based on 100 parts by weight of the rubber-based pressure-sensitive adhesive composition.
The first curing agent and the second curing agent may each be 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber-based resin.
The weight ratio of the first curing agent and the second curing agent may be from 5: 1 to 1: 5.
An ultraviolet light stabilizer, a photoinitiator, a thermal initiator, an antioxidant, a filler, and a plasticizer.
In one embodiment of the present invention, there is provided a rubber-based pressure-sensitive adhesive in which the rubber-based adhesive composition is cured.
The curing degree (gel content) of the rubber adhesive may be 40% to 60%.
Since the rubber-based pressure-sensitive adhesive composition according to the present invention contains a thiol compound as a curing agent, the rubber-based pressure-sensitive adhesive according to the present invention is excellent in wettability and durability. Therefore, by applying the rubber adhesive according to the present invention to a touch material or an electronic device, the durability of a next generation device such as a touch panel or an OLED can be increased.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the ratio of absorbance of infrared rays according to the weight ratio of HDDA and PEMP with an FT-IR spectrophotometer. FIG.
The inventors of the present invention confirmed that a rubber-based pressure-sensitive adhesive composition having excellent durability can be prepared by including a thiol compound as a curing agent in a rubber-based pressure-sensitive adhesive composition while studying a rubber-based pressure-sensitive adhesive composition having excellent durability.
Hereinafter, the present invention will be described in detail.
The present invention relates to a rubber-based resin; A first curing agent; And a second curing agent, wherein the second curing agent is a thiol compound.
Since the rubber-based resin has a low glass transition temperature (Tg), is composed only of hydrocarbons, and has a very low surface energy, the rubber-based pressure-sensitive adhesive composition comprising a rubber- This is an excellent advantage.
The rubber-based resin may be at least one selected from the group consisting of styrene-butadiene-styrene (SBS) rubber, styrene-butadiene (SB) rubber, styrene-isoprene-styrene (SIS) rubber, styrene- Rubber (LATEX) and butyl-based rubber, and it is more preferable that it is a styrene-butadiene-styrene (SBS) -based rubber.
The styrene-butadiene-styrene (SBS) rubber is a kind of butadiene-based rubber, and has a hard segment property as compared with other rubbers such as isoprene rubber such as styrene-isoprene-styrene (SIS) Therefore, it is particularly excellent in high temperature durability during curing. Further, styrene-butadiene-styrene (SBS) type rubbers are most preferable because the degree of curing is different even when the same amount of the same hardening agent is added.
At this time, the rubber-based resin is preferably 50 parts by weight to 80 parts by weight with respect to 100 parts by weight of the rubber-based pressure-sensitive adhesive composition, but is not limited thereto. If the amount of the rubber-based resin is less than 50 parts by weight based on 100 parts by weight of the rubber-based pressure-sensitive adhesive composition, the amount of the solvent is relatively increased even though the coating property is not problematic. There is a problem in curing when the solvent which is not volatilized remains. When the rubber-based resin is used in an amount of more than 80 parts by weight based on 100 parts by weight of the rubber-based pressure-sensitive adhesive composition, there is a problem in coatability due to an increase in viscosity.
The first curing agent may be a UV curable resin having good compatibility with a rubber-based resin. For example, it may be selected from an acrylate resin, a methacrylate resin, an isocyanate resin, a melamine resin, a urethane resin, an epoxy resin, an acid anhydride, a polyamine resin and a polymer containing a carboxyl group.
The first curing agent may be selected from the group consisting of 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, tetramethylol Tetramethylol methane triacrylate, trimethylolpropane triacrylate, 1,6-bis (3-acryloyloxy) -2-hydroxypropyloxy) hexane [ -2-hydroxypropyl) hexane, polyethylene glycol diacrylate, pentaerythritol triacrylate, and hexamethylene diisocyanate urethane prepolymer. It is preferably one or more, more preferably 1,6-hexanediol diacrylate It recommended one, and the like.
The 1,6-hexanediol diacrylate has a weight average molecular weight (Mw) of 226.27 and a weight average molecular weight (Mw) of about 200. At this time, if the molecular structure is too long, the curing becomes too loose and durability is deteriorated. If the molecular structure is too short, the curing becomes too dense and the peeling strength is lowered.
The second curing agent may be a thiol compound, and the thiol compound may be a compound having two or more primary thiol groups in the molecule.
The thiol compound is classified according to the number of the -SH functional group and the position where the functional group is attached, but it is preferable to have four primary thiol groups attached to the 2,3,4,6-terminus in the molecule, but not limited thereto. In the present invention, pentaerythritol tetrakis (3-mercaptobutylate) was used as a tetra-fuctional primary thiol (PEMP) as a thiol compound. At this time, the weight average molecular weight of pentaerythritol tetrakis was 544.76.
In this case, as the curing agent, the first curing agent and the second curing agent may each be 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber-based resin. If the first curing agent and the second curing agent are each less than 0.1 part by weight based on 100 parts by weight of the rubber-based resin, there is a problem that the curing degree becomes extremely low and can be uncured and the high temperature durability may be very low. When the amount of the second curing agent is more than 5 parts by weight based on 100 parts by weight of the rubber-based resin, the rubber-based pressure-sensitive adhesive to be produced is hardened, resulting in deterioration of physical properties such as peel strength.
Preferably, the weight ratio of the first curing agent and the second curing agent is adjustable, but the weight ratio of the first curing agent and the second curing agent is preferably 5: 1 to 1: 5, The weight ratio of the curing agent is more preferably 3: 1 to 1: 3, and the weight ratio of the first curing agent and the second curing agent is most preferably 1: 3, but is not limited thereto. If the content of the first curing agent is too large, there is a problem that the degree of curing of the rubber-based pressure sensitive adhesive to be produced is excessively increased to deteriorate physical properties such as peel strength. When the content of the second curing agent is relatively large, There is a problem of deterioration.
The pressure-sensitive adhesive composition may further comprise at least one selected from the group consisting of a pressure-sensitive adhesive, a UV stabilizer, a photoinitiator, a thermal initiator, an antioxidant, a filler and a plasticizer in addition to the rubber- The additive may be appropriately adjusted within a range that does not impair the physical properties of the pressure-sensitive adhesive composition, and further includes additives such as a pigment, an ultraviolet stabilizer, a dispersant, a defoaming agent, a thickener, a plasticizer, a tackifier resin, a silane coupling agent, It is possible.
Also provided is a rubber-based pressure-sensitive adhesive in which the rubber-based adhesive composition according to the present invention is cured.
The curing degree (gel content) of the rubber adhesive may be 40% to 60%. If the degree of curing (gel content) of the rubber adhesive is less than 40%, the durability of the rubber adhesive tends to deteriorate. If the degree of curing (gel content) of the rubber adhesive exceeds 60%, the rubber adhesive tends to be hard. There is a problem that the physical properties are deteriorated
In addition, the rubber-based pressure-sensitive adhesive composition can be formed by curing the rubber-based pressure-sensitive adhesive composition, and the thickness of the rubber-based pressure-sensitive adhesive composition can be adjusted to about 10 탆 to about 70 탆. By maintaining the thickness of the rubber adhesive in the above range, a sufficient adhesive force can be secured and the process conditions can be stably maintained.
The rubber-based pressure-sensitive adhesive composition can ensure heat resistance through curing of the rubber-based pressure-sensitive adhesive composition, wherein the curing of the rubber-based pressure-sensitive adhesive composition is carried out using an energy source selected from the group consisting of heat, ultraviolet light, visible light, infrared radiation, And the like. In the present invention, the ultraviolet light (UV) is used to cure the rubber adhesive composition, which is economically advantageous compared with the case of using other energy sources.
Since the rubber-based pressure-sensitive adhesive composition according to the present invention contains a thiol compound as a curing agent, the rubber-based pressure-sensitive adhesive according to the present invention is excellent in wettability and durability. Therefore, by applying the rubber adhesive to a touch material or an electronic device, durability of a next generation device such as a touch panel or an OLED can be increased.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.
[ Example ]
Example One
To 100 g of a styrene-butadiene-styrene (SBS) rubber, 0.2 g of 1,6-hexanediol diacrylate (HDDA) as a curing agent and 0.1 g of tetra-functional primary thiol (KarenzMT TM PE1) was added, 80 g of toluene was added as a solvent, and the mixture was sufficiently stirred to prepare a rubber-based pressure-sensitive adhesive composition.
Example 2
0.4 g of 1,6-hexanediol diacrylate (HDDA) as a curing agent and 0.4 g of tetra-functional primary thiol (KarenzMT TM PE1) was added to the pressure-sensitive adhesive composition of Example 1, to prepare a rubber-based pressure-sensitive adhesive composition.
Example 3
0.6 g of 1,6-hexanediol diacrylate (HDDA) as a curing agent and 0.6 g of tetra-functional primary thiol (KarenzMT TM PE1) as a crosslinking agent was added to the rubber-based pressure-sensitive adhesive composition.
Comparative Example One
A rubber-based pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that no curing agent was added at all.
Comparative Example 2
A pressure sensitive adhesive rubber composition was prepared in the same manner as in Example 1, except that 0.4 g of 1,6-hexanediol diacrylate (HDDA) alone was added as a curing agent.
Comparative Example 3
As a curing agent, tetra-functional primary thiol (PEMP (KarenzMT TM PE1) was added in an amount of 0.4 g, a rubber-based pressure-sensitive adhesive composition was prepared.
Experimental Example
1. Measurement of hardness (gel content)
On the PET release film, the rubber-based pressure-sensitive adhesive compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were coated with a knife coater (coating thickness: 50 占 퐉). Then, the coated rubber-based pressure-sensitive adhesive composition was placed under a metal halide lamp and irradiated with ultraviolet rays of 10 mW / cm for about 3 minutes to cure the rubber-based pressure-sensitive adhesive. The prepared rubber adhesive was cut into 1 inch × 1 inch (length × length), and the weight of the specimen was measured. 50 ml of toluene solvent was added to the PET bottle, and the mixture was stored at room temperature for 24 hours. A full-swelled rubber adhesive was applied to a prepared 130 mm x 130 mm 200 mesh, dried in an oven at 110 DEG C for 4 hours, and then weighed. The final gel content was measured by calculating the difference between the weight of the first adhesive and the weight of the latter adhesive.
2. Durability measurement
The rubber-based pressure-sensitive adhesive, which is a cured product of the rubber-based pressure-sensitive adhesive composition prepared in Examples 1 to 3 and Comparative Examples 1 to 3, was cut into 1 inch x 1 inch (width x length), and the specimen was put into an autoclave at 90 ° C, To measure the separation time of the substrate and the rubber adhesive.
3. Peel strength measurement
A rubber pressure-sensitive adhesive, which is a cured product of the rubber-based pressure-sensitive adhesive composition prepared in Examples 1 to 3 and Comparative Examples 1 to 3, was cut into pieces of 1 inch x 10 cm (width x length) (Yulchon Chemical Co., Ltd. SG00), and was attached to and reciprocated twice with a 2 kg roller. After 30 minutes passed at a room temperature (23 ° C), a peel strength meter was used to measure the peeling speed And the peel strength was measured at a peel angle of 180 degrees.
The results of the measurement of the degree of curing (gel content), durability and peel strength are summarized in Table 1 below.
(g)
(g)
(min)
(kgf / in)
* HDDA: 1,6-hexanediol diacrylate
* PEMP: tetra-fuctional primary thiol
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the absorbance ratio of infrared wave number according to the weight ratio of HDDA and PEMP with an FT-IR spectrophotometer. FIG.
As shown in Table 1, it was confirmed that the rubber-based pressure-sensitive adhesive composition of Examples 1 to 3 contains a thiol compound as a curing agent and therefore has excellent durability due to high wetting and high degree of curing. It was also confirmed that the peel strength of the rubber-based pressure-sensitive adhesive compositions according to Examples 1 to 3 was maintained at an appropriate level.
1, when the weight ratio of HDDA and PEMP as a curing agent was 1: 3 as in the case of the rubber-based pressure-sensitive adhesive composition according to Example 1, the weight ratio of HDDA and PEMP as a curing agent, as in the case of the rubber- 1, it was confirmed that the durability was further improved because the degree of curing was higher because the absorbance was considerably high at a wave number of about 1750 cm -1 . At this time, the control group had a high solids content of the rubber-based pressure-sensitive adhesive composition in the rubber-based pressure-sensitive adhesive composition, which corresponds to a high absorbance at a wave number of about 1750 cm -1 .
It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (10)
A first curing agent; And
A second curing agent,
Wherein the first curing agent is selected from an acrylate resin and a methacrylate resin,
The second curing agent is a thiol compound,
The weight ratio of the first curing agent and the second curing agent is 5: 1 to 1: 5,
Wherein the first curing agent and the second curing agent are each 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber-based resin
Based pressure-sensitive adhesive composition.
The rubber-based resin may be at least one selected from the group consisting of styrene-butadiene-styrene (SBS) rubber, styrene-butadiene (SB) rubber, styrene-isoprene-styrene (SIS) rubber, styrene- Rubber (LATEX) and butyl-based rubber
Based pressure-sensitive adhesive composition.
The first curing agent may be selected from the group consisting of 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, tetramethylol Tetramethylolmethane triacrylate, trimethylolpropane triacrylate, 1,6-bis (3-acryloyloxy) -2-hydroxypropyloxy) hexane 2-hydroxypropyl) hexane], polyethylene glycol diacrylate, and pentaerythritol triacrylate. [0030]
Based pressure-sensitive adhesive composition.
The thiol compound is a compound having two or more primary thiol groups in the molecule
Based pressure-sensitive adhesive composition.
The rubber-based resin is used in an amount of 50 to 80 parts by weight per 100 parts by weight of the rubber-
Based pressure-sensitive adhesive composition.
An ultraviolet stabilizer, a photoinitiator, a thermal initiator, an antioxidant, a filler, and a plasticizer,
Based pressure-sensitive adhesive composition.
The curing degree (gel content) of the rubber-based pressure-sensitive adhesive is 40% to 60%
Rubber adhesive.
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| KR1020140049735A KR101775759B1 (en) | 2014-04-25 | 2014-04-25 | Adhesive composition with excellent durability |
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| KR1020140049735A KR101775759B1 (en) | 2014-04-25 | 2014-04-25 | Adhesive composition with excellent durability |
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| KR101775759B1 true KR101775759B1 (en) | 2017-09-07 |
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| KR102112666B1 (en) * | 2017-12-29 | 2020-05-20 | (주)케이비어드히시브스 | Heat resistant rubber adhesive composition and adhesive tape containing the same |
| KR102094963B1 (en) * | 2018-07-12 | 2020-03-30 | 율촌화학 주식회사 | Adhesive film and adhesive tape for moisture protection, and method for producing the same |
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