KR102392725B1 - Acrylic adhesive composition, acrylic adhesives thermally cured therefrom, a decoration glass panel using the same - Google Patents

Abstract

The present invention relates to a polymerization unit made of an alkyl (meth)acrylate, a polymerized unit made of hydroxy (meth)acrylate, a polymerized unit made of alkoxy (meth)acrylate, and a polymerized unit made of hydroxyalkyl (meth)acrylamide. a thermosetting acrylic copolymer comprising; And it discloses an acrylic pressure-sensitive adhesive composition comprising a photocurable urethane acrylic oligomer having 3 to 6 photoreactive functional groups.
The acrylic pressure-sensitive adhesive made of a thermosetting product of the acrylic pressure-sensitive adhesive composition of the present invention can be easily removed and reworked when a defect occurs in the manufacturing process of the decorative glass panel, and the side lifting phenomenon of the plastic decorative sheet on the curved glass and the adhesive layer The pressing phenomenon is improved. In addition, after application to a decorative glass panel, the acrylic pressure-sensitive adhesive of the present invention exhibits low shrinkage and excellent adhesion during photocuring.

Description

ACRYLIC ADHESIVE COMPOSITION, ACRYLIC ADHESIVES THERMALLY CURED THEREFROM, A DECORATION GLASS PANEL USING THE SAME}

The present invention relates mainly to an acrylic pressure-sensitive adhesive composition interposed between a decorative plastic sheet and a glass panel and used as an adhesive for bonding them, an acrylic pressure-sensitive adhesive made of a thermosetting product thereof, and a decorative glass panel bonded using the same.

So-called decorative glass panels in which decorative plastic sheets, which are interior finishing materials, in which various types of patterns are selectively printed on the surface of glass panels, are bonded are used in TVs, refrigerator fronts, automobiles, and the like.

For example, as a display larger than 60 inches is used indoors and outdoors, the decorative glass panel supporting the display is also enlarged and used more frequently to suit the space of use. That is, a back cover is made using a decorative glass panel, or an arched wall is formed to fix the display panel. In addition, the case of manufacturing the front glass of a refrigerator or the curved glass of a car with a decorative glass panel is increasing.

A decorative glass panel is manufactured by applying a photocurable adhesive to a decorative plastic sheet, then laminating the glass panel and curing the adhesive by irradiating light. In the process of laminating glass panels in manufacturing decorative glass panels, defects such as air bubbles or thread spread, side lifting of the plastic decorative sheet on curved glass, and pressing of the adhesive layer may occur. These defects will increase. Only if the adhesive can be completely removed in the event of a defect can the expensive glass panels be reused and reworked.

In addition, the photocured adhesive layer applied to the manufactured decorative panel needs to have low shrinkage and good adhesion.

Accordingly, an object of the present invention is to provide an adhesive composition that is easy to completely remove when a defect occurs in the manufacturing process of a decorative glass panel, and an adhesive made of a thermosetting product thereof.

Another technical problem to be solved by the present invention is to provide an adhesive composition and a thermosetting adhesive having improved side lifting phenomenon and pressure-sensitive adhesive layer when bonding a curved glass panel and a plastic decorative sheet, in particular, in addition to the above object. .

Another technical problem to be solved by the present invention is to provide a decorative glass panel that is firmly adhered to a plastic decorative sheet and has improved side lifting and pressing of the adhesive layer of the plastic decorative sheet.

In order to solve the above technical problem, the acrylic pressure-sensitive adhesive composition according to the first embodiment of the present invention is a polymerization unit made of alkyl (meth) acrylate, a polymer unit made of hydroxy (meth) acrylate, and alkoxy (meth) acryl a thermosetting acrylic copolymer comprising a polymer unit made of a rate and a polymer unit made of hydroxyalkyl (meth) acrylamide ; and

and a photocurable urethane acrylic oligomer having 3 to 6 photoreactive functional groups.

According to the second embodiment of the present invention, in the first embodiment, the content of the thermosetting acrylic copolymer may be 55 to 85 parts by weight based on 100 parts by weight of the solid content, and the content of the photocurable urethane acrylic oligomer is 5 to 25 It may be parts by weight.

According to a third embodiment of the present invention, in at least one embodiment of the first embodiment or the second embodiment, the weight ratio of the thermosetting acrylic copolymer and the photocurable urethane acrylic oligomer is 3:1 to 9:1 days can

According to a fourth embodiment of the present invention, in at least one embodiment of the first to third embodiments, the polymerization unit of the alkyl (meth)acrylate, the polymerization of the hydroxy (meth)acrylate The content of the unit, the polymerized unit made of alkoxy (meth)acrylate and the polymerized unit made of hydroxyalkyl (meth)acrylamide is 50 to 80 wt% and 5 to 20 wt%, respectively, based on the total polymerized units constituting the copolymer. %, 5 to 20% by weight and 2 to 20% by weight.

According to a fifth embodiment of the present invention, in at least one embodiment of the first to fourth embodiments, the polymerization unit made of the alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) ) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl ( meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, At least one selected from the group consisting of lauryl (meth) acrylate and tetradecyl (meth) acrylate, and the polymerization unit made of hydroxy (meth) acrylate is 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth) ) at least one selected from the group consisting of acrylate, 2-hydroxyethylene glycol (meth) acrylate, and 2-hydroxypropylene glycol (meth) acrylate, and the polymer unit made of the alkoxy (meth) acrylate is At least one selected from the group consisting of ethoxyethoxy ethyl (meth) acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, and methoxy polyethylene glycol acrylate, and the hydroxyalkyl (meth) acrylamide may be at least one selected from the group consisting of hydroxyethyl (meth)acrylamide, hydroxymethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, and hydroxybutyl (meth)acrylamide, and more specifically As, the polymerization unit made of the alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) acrylate and t-butyl ( At least two or more selected from the group consisting of meth) acrylate and sec-butyl (meth) acrylate, wherein the hydroxy (meth) acrylate polymerization unit is 2-hydroxyethyl (meth) acrylate, and The polymerization unit made of alkoxy (meth)acrylate may be ethoxyethoxy ethyl (meth)acrylate, and the hydroxyalkyl (meth)acrylamide may be hydroxyethyl (meth)acrylamide.

According to the sixth embodiment of the present invention, in at least one embodiment of the first to fifth embodiments, the weight average molecular weight of the photocurable urethane acrylic oligomer may be 500 to 3,000 g/mol.

According to the seventh embodiment of the present invention, in at least one embodiment of the first to sixth embodiments, the photocurable urethane acrylic oligomer is a reaction between an isocyanate-based compound and hydroxyalkyl (meth)acrylamide. It may be derived, and more specifically, the photocurable urethane acrylic oligomer may be a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, or a mixture thereof.

In Formula 1, R ₁ is hydrogen or a methyl group.

The above-described acrylic pressure-sensitive adhesive composition may be heat-cured to prepare an acrylic pressure-sensitive adhesive, and the adhesive strength of the acrylic pressure-sensitive adhesive may be 0.3 to 1.7 Kgf/in with respect to tempered glass at room temperature, and light compared to the glass transition temperature before photocuring of the acrylic pressure-sensitive adhesive The glass transition temperature after heating can be increased by 60 to 100 °C.

Such an acrylic pressure-sensitive adhesive may be manufactured into a decorative plastic sheet, a glass panel, and a decorative glass panel by being interposed therebetween and photocuring.

The acrylic pressure-sensitive adhesive made of a thermosetting product of the acrylic pressure-sensitive adhesive composition of the present invention is easily removed when a defect occurs in the manufacturing process of the decorative glass panel, so that the rework operation is possible.

In addition, in the decorative glass panel manufactured using the acrylic pressure-sensitive adhesive of the present invention, the side lifting phenomenon of the plastic decorative sheet with respect to the curved glass and the pressing phenomenon of the adhesive layer are improved.

In addition, the acrylic pressure-sensitive adhesive of the present invention exhibits a low shrinkage during photocuring and excellent adhesion.

1 is a cross-sectional view schematically illustrating a step of attaching a thermosetting acrylic pressure-sensitive adhesive to one surface of a decorative plastic sheet and then bonding to a curved glass panel according to an embodiment of the present invention.
2 is a view schematically showing a process of laminating and bonding decorative plastic sheets-sheets containing an acrylic adhesive-curved glass panels sequentially in a roll to roll process according to another embodiment of the present invention.
3 is a schematic cross-sectional view of a decorative glass panel according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

In the present invention, "acrylic" means branched or unbranched acrylic acid or methacrylic acid or a derivative thereof.

“(meth)acrylate” and “(meth)acrylamide” are meant to include both acrylate and methacrylate, and acrylamide and methacrylamide, respectively.

Alkyl (meth) acrylate means (meth) acrylate having an alkyl group, hydroxy (meth) acrylate means (meth) acrylate having a hydroxyl group, alkoxy (meth) acrylate having an alkoxy group ( It means meth)acrylate, and hydroxyalkyl (meth)acrylamide means (meth)acrylamide having a hydroxyalkyl group.

The photocurable urethane (meth)acrylic oligomer having 3 to 6 photoreactive functional groups means a (meth)acrylic oligomer having 3 to 6 photoreactive functional groups and a urethane bond.

Hereinafter, the acrylic pressure-sensitive adhesive composition according to the present invention will be described.

The acrylic pressure-sensitive adhesive composition of the present invention comprises a polymer unit made of alkyl (meth) acrylate, a polymer unit made of hydroxy (meth) acrylate, a polymer unit made of alkoxy (meth) acrylate, and hydroxyalkyl (meth) acrylamide. a thermosetting acrylic copolymer comprising a polymerized unit ; and a photocurable urethane acrylic oligomer having 3 to 6 photoreactive functional groups.

The present inventors have found that when a defect occurs in the manufacturing process of a decorative glass panel, it is easily removed and reworked, and the side lifting phenomenon of the plastic decorative sheet for glass, particularly curved glass, and the pressing phenomenon of the adhesive layer are improved, and decoration As a result of examining and verifying the combination of adhesive components exhibiting excellent physical properties even after application to a glass panel, it was confirmed that these effects are expressed when the pressure-sensitive adhesive composition of the above-described configuration is used as an adhesive component, and the present invention has been completed.

In the acrylic pressure-sensitive adhesive composition of the present invention, the polymerization unit made of alkyl (meth)acrylate contained in the thermosetting acrylic copolymer imparts a low glass transition temperature and hydrophobicity to the copolymer, thereby improving the wettability of the adherend surface. do. Examples of the alkyl (meth) acrylate include (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, more specifically methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) ) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate and tetra At least one selected from the group consisting of decyl (meth) acrylate, or two or more alkyl (meth) acrylates such as a combination of methyl (meth) acrylate and butyl (meth) acrylate may be used in combination, but not limited thereto does not More preferably, the polymerization unit made of alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( It may be at least two or more selected from the group consisting of meth)acrylate, t-butyl (meth)acrylate, and sec-butyl (meth)acrylate.

The content of the polymer unit made of alkyl (meth) acrylate may be 50 to 80 wt %, more preferably 50 to 75 wt %, based on the total polymer unit constituting the thermosetting acrylic copolymer in terms of the above-mentioned effects. may be, and more specifically, may be 55 to 70% by weight.

In the acrylic pressure-sensitive adhesive composition of the present invention, the polymer unit made of hydroxy (meth) acrylate contained in the thermosetting acrylic copolymer has a polarity due to the hydroxy group. improve compatibility. The polymerization unit made of hydroxy (meth) acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acryl It may be at least one selected from the group consisting of rate, but is not limited thereto. Particularly preferably, it may be 2-hydroxyethyl (meth)acrylate.

The content of the polymer unit made of hydroxy (meth) acrylate may be 5 to 20 wt %, more preferably 10 to 20 wt %, based on the total polymer unit constituting the thermosetting acrylic copolymer in terms of the above-described effect. %, more specifically 10 to 15% by weight.

In the acrylic pressure-sensitive adhesive composition of the present invention, the polymer unit made of alkoxy (meth) acrylate contained in the thermosetting acrylic copolymer is provided with cohesive force to the copolymer due to the alkoxy group provided in the side chain, so that the copolymer is a separate heat curing agent It improves the cohesive force in the adhesive layer even without it. Accordingly, when the pressure-sensitive adhesive composition is coated, it is easily processed into a film. Examples of the alkoxy (meth)acrylate include (meth)acrylate having an alkoxy group having 2 to 30 carbon atoms. More specifically, ethoxyethoxyethyl (meth)acrylate, polypropylene glycol monoacrylate, polyethylene It may be at least one selected from the group consisting of glycol monoacrylate and methoxypolyethylene glycol acrylate, but is not limited thereto. Particularly preferably, it may be ethoxyethoxy ethyl (meth)acrylate.

The content of the polymer unit made of alkoxy (meth) acrylate may be 5 to 20 wt %, more preferably 5 to 15 wt %, based on the total polymer unit constituting the thermosetting acrylic copolymer in terms of the above-mentioned effects. may be, and more specifically, may be 10 to 15% by weight.

In the acrylic pressure-sensitive adhesive composition of the present invention, the polymer unit made of hydroxyalkyl (meth)acrylamide contained in the thermosetting acrylic copolymer increases the adhesive force of the copolymer, thereby preventing the occurrence of lifting on the adherend. In addition, it prevents phase separation by improving compatibility with a photocurable urethane (meth)acrylic oligomer to be described later. Examples of the hydroxyalkyl (meth)acrylamide include (meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms. More specifically, hydroxyethyl (meth)acrylamide, hydroxymethyl (meth) It may be at least one selected from the group consisting of acrylamide, hydroxypropyl (meth)acrylamide, and hydroxybutyl (meth)acrylamide, However, the present invention is not limited thereto. Particularly preferably, it may be hydroxyethyl (meth)acrylamide.

The content of the polymer unit made of hydroxyethyl (meth) acrylamide may be 2 to 20 wt %, more preferably 5 to 15 wt %, based on the total polymer units constituting the thermosetting acrylic copolymer in terms of the above-described effects. It may be % by weight, and more specifically, may be 5 to 10% by weight.

Of course, in addition to the above-described polymer units, the thermosetting acrylic copolymer may further include other polymer units within the limit not impairing the object of the present invention. The above-described thermosetting acrylic copolymer may have a weight average molecular weight of 500,000 to 1,200,000 g/mol.

On the other hand, the acrylic pressure-sensitive adhesive composition of the present invention includes a photocurable urethane acrylic oligomer having 3 to 6 photoreactive functional groups. These oligomers have good compatibility with the aforementioned thermosetting acrylic copolymer.

Since the photocurable urethane acrylic oligomer contains 3 to 6 photoreactive functional groups, the sagging phenomenon in which the adhesive layer spreads sideways or aggregates to the edges during slitting or lamination is controlled even in the B-stage before photocuring. In addition, since the photocurable urethane acrylic oligomer maintains a solid state even before photocuring after thermal drying coating, it does not accelerate the flowability of the adhesive. That is, according to the present invention, the pressure-sensitive adhesive composition comprising the copolymer and the photocurable urethane acrylic oligomer according to the present invention has good compatibility in the B-stage and maintains a transparent state, and after light curing, an interpenetrating polymer network is formed. well formed.

The photocurable urethane acrylic oligomer may be derived from a reaction between an isocyanate-based compound and hydroxyalkyl (meth)acrylamide.

As the isocyanate-based compound, for example, as a structure having an isocyanurate functional group, DURANATE TPA-100, DURANATE TKA-100, DURANATE MFA-75B, DURANATE TMHG-80B (Asahi Kasei), CORONATE HXR (hexamethylene diisocyanate) isocyanurate of Tosoh), TAKENATE D-127N (isocyanurate of hydrogenated xylene diisocyanate, Mitsui Chemicals), VESTANAT T1890/100 (trimer of isocyanurate of isophorone diisocyanate, Evonik) and the like can be exemplified. 1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione, 1,3,5-tri-[ which is preferably a trimer of isocyanurate of isophorone diisocyanate 5-isocyanato-1,3,3,3-trimethylcyclohexyl]methyl].

For the hydroxyalkyl (meth)acrylamide, the compound described above in the polymerization unit of the thermosetting acrylic copolymer may be used.

The photocurable urethane acrylic oligomer may have a weight average molecular weight of 500 to 3,000 g/mol, and in particular, a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, or a mixture thereof.

<Formula 1>

In Formula 1, R ₁ is hydrogen or a methyl group.

<Formula 2>

In the acrylic pressure-sensitive adhesive composition of the present invention, the content of the above-mentioned thermosetting acrylic copolymer may be 55 to 85 parts by weight, more preferably 65 to 80 parts by weight, based on 100 parts by weight of the solid content, and the content of the photocurable urethane acrylic oligomer Silver may be 5 to 25 parts by weight, more preferably 5 to 20 parts by weight.

In addition, the weight ratio of the thermosetting acrylic copolymer and the photocurable urethane acrylic oligomer may be 3:1 to 9:1, and more preferably 4:1 to 8:1. When these content ranges and ratios are satisfied, the desired effect of the acrylic pressure-sensitive adhesive composition of the present invention is efficiently and balanced.

Of course, in addition to the above-described photocurable urethane acrylic oligomer, the acrylic pressure-sensitive adhesive composition may further include other photocurable oligomers without impairing the object of the present invention.

The acrylic pressure-sensitive adhesive composition of the present invention may further include a photoinitiator to form a photocured adhesive layer after being interposed between the decorative plastic sheet and the glass panel. As the photoinitiator, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide (2,4,6-Trimethylbenzoyl-diphenyl-phosphineoxide, TPO)-based compound, acyl phosphine-based compound One or more types of known photoinitiators may be used, but the present invention is not limited thereto. Commercially available examples of the photoinitiator can be exemplified by Irgacure184, Irgacure1173, Irgacure369, Irgacure651, Irgacure TPO, Irgacure2100, Irgacure2022 and the like sold by BASF.

The acrylic pressure-sensitive adhesive composition of the present invention may further include a known additive such as a silane coupling agent. As a silane coupling agent, KBM-303 (2-(3,4 epoxycyclohexyl)-ethyltrimethoxysilane), KBM-403 (3-Glycidoxypropyl trimethoxy), KBM-402 (3-Glycidoxypropylmethyldiethoxysilane) from Shin-Etsu Corporation of Japan, and methacrylic KBM-502 (3-Methacryloxypropylmethyldimethoxysilane), KBM-503 (3-Methacryloxypropyltriethoxysilane), mercapto-based KBM-803 (3-Mercaptopropyl trimethoxysilane), etc. can be exemplified.

The acrylic pressure-sensitive adhesive composition of the present invention is obtained by applying a solution of the acrylic pressure-sensitive adhesive composition prepared by using the solvent included in the synthesis of the above-described thermosetting acrylic copolymer or adding a solvent to the substrate on the substrate, and then thermally drying the acrylic pressure-sensitive adhesive composition. A thermosetting acrylic pressure-sensitive adhesive, for example, may be prepared to a thickness of 20 to 30 μm. That is, for example, the pressure-sensitive adhesive composition may be directly applied to and dried on a decorative plastic sheet to form the pressure-sensitive adhesive layer, or may be prepared by coating and drying the pressure-sensitive adhesive composition on a known release film. The adhesive strength of the acrylic pressure-sensitive adhesive prepared in this way is 0.3 to 1.7 Kgf/in with respect to tempered glass at room temperature. It is preferable in terms of ease of rework in case of defects while adhering well without side lifting of the decorative plastic sheet to the glass panel.

In addition, the glass transition temperature after photocuring compared to the glass transition temperature before photocuring of the acrylic pressure-sensitive adhesive is preferably increased by 60 to 100 °C. At this time, the glass transition temperature of the acrylic pressure-sensitive adhesive may be -20 to -40 °C, more preferably -30 to -35 °C, and the glass transition temperature after photocuring may be 40 to 50 °C. When the glass transition temperature rises to the above-mentioned range after photocuring in the B-stage before photocuring, the wettability at room temperature is good, so it is easy to effectively adhere to the tempered glass having a curved surface, and after photocuring, the shrinkage rate is reduced Stability is improved. On the other hand, if the glass transition temperature after photocuring is 40 °C or higher, it is possible to prevent the formation of press marks due to foreign substances during operation.

The acrylic pressure-sensitive adhesive of the present invention is interposed between a known decorative plastic sheet such as polyvinyl chloride, polypropylene, or polyester and a glass panel such as tempered glass to adhere them to each other. If the same defects occur between the bonded plastic sheet and tempered glass, such as air bubbles or thread spread, side lifting of the plastic decorative sheet on the curved glass, or the pressing of the adhesive layer, the decorative plastic sheet and the adhesive layer can be easily removed to remove the glass. Make sure that no foreign substances remain on the panel. If defects do not occur, by irradiating UV with a light amount of 500 to 2,000 mJ/cm ² to the bonded decorative glass panel, and photocuring the acrylic pressure-sensitive adhesive into an adhesive layer having adhesive strength, to produce a finished decorative glass panel. can

As such, in the present invention, 'adhesion' and 'adhesion' have distinct meanings. 'Adhesion' refers to a state in which it can adhere well and can be easily removed at the same time, that is, a state that can be reworked. On the other hand, 'bonding' refers to a state in which physically or chemically bonded objects form an integrated state, and rework is not possible due to strong adhesive force.

1 is a cross-sectional view schematically illustrating a method of forming or attaching a sheet 20 made of an acrylic pressure-sensitive adhesive to a decorative plastic sheet 10 and then bonding the sheet 20 to a curved glass panel 30 . As described above, by first forming the adhesive sheet 20 on the decorative plastic sheet and then bonding to the curved glass panel 30 , the decorative glass panel can be manufactured.

2 is a view schematically illustrating a process of laminating and bonding a decorative plastic sheet 10 - an acrylic adhesive sheet 20 - a curved glass panel 30 in sequence through a roll-to-roll process. In FIG. 2 , the glass is transported by a lower roll, and the decorative plastic sheet 10 on which the adhesive sheet 20 is formed on one surface from the top by a separately installed roll is formed by the adhesive sheet 20 and the curved glass panel 30 . The decorative plastic sheet 10 - the adhesive sheet 20 - the curved glass panel 30 may be sequentially stacked by being transported to meet in the bonding direction.

3 is a schematic cross-sectional view of a finished decorative glass panel.

After forming a laminate such that the decorative plastic sheet 10 - the adhesive sheet 20 - the curved glass panel 30 is sequentially laminated, the adhesive sheet is well attached so that problems such as air bubbles and thread spread do not appear. An acrylic adhesive layer 40 is formed by photo-curing the sheet 20 by irradiating light, and a decorative glass panel 100 in which a decorative plastic sheet 10 - an acrylic adhesive layer 40 - a curved glass panel 30 is laminated is formed can do. However, if a defect occurs after forming a laminate such that the decorative plastic sheet-adhesive sheet-glass panel is sequentially laminated according to FIG. It can be peeled off (reworked) and recycled.

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiment described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

<Measurement of weight average molecular weight>

After collecting the prepared thermosetting acrylic copolymer, it was put into a 50 ml glass bottle together with tetrahydrofuran and dissolved to prepare a sample with a 1 wt% solution. After filtering this sample through a 0.45 μm filter, it was measured using GPC (Aginent 1260) at a flow rate of 1.00 mL/min and a column temperature of 35 °C. PLgel Mixed A and B were used as columns for calibration and the weight average molecular weight was measured.

<Adhesive force and adhesive force evaluation>

After the elapse of time according to Table 1 on the tempered glass, the adhesive force or the adhesive force was measured at 25 °C and 50 RH% using a measuring device (AR-1000, Chem Instruments), respectively. An adhesive sheet adhered or adhered to tempered glass was prepared with a sample size of 25.4Х300 mm, performed at a speed of 300 mm/min under a 180° peeling angle, and the average value of 5 repeated measurements was obtained, and the adhesive force or adhesive force (gf/in ) was found.

<Evaluation of rework characteristics>

After laminating the adhesive sheet on the tempered glass, it was left at room temperature (25 °C) for 30 minutes, and then the process of peeling the tempered glass was repeated 10 times. By observing whether any residues were left on the tempered glass, it was judged as "residue generation" when residues were left at least once, and "good" when no residues were left.

<Evaluation of side lifting>

After bonding the adhesive layer between the decorative plastic sheet and the curved tempered glass, we observed whether the adhesive layer floats on the side of the tempered glass when the edge is cut using a commercially available cutter knife. In the case of reattachment, it was checked whether a stop-line mark came out from the lifting part. The evaluation criteria are as follows.

Excellent: No lifting occurs even when the adhesive layer on the side is removed.

Insufficient: Side lifting occurred, but no stop-line marks were observed when reattached.

Defect: Side lifting occurred, and stop-line marks were observed even after reattachment.

<Measurement of storage modulus modulus>

The viscoelastic behavior of the adhesive was measured using an ARES G2 Rheometer (TA instruments). The storage modulus modulus at 25 °C was measured by the temperature sweep method while the temperature was raised from -60 °C to 100 °C at a rate of 5 °C/min. When measuring the storage modulus, the axial force was 2N, the strain was 10%, and the rotational speed was 1 rad/sec, and it was measured at 0.159 Hz.

<Pressure degree evaluation>

A thin wire with a diameter of 1 mm and a length of 1 cm was fixed to the microscope plate, and then a decorative plastic sheet/adhesive layer/curved tempered glass cementation panel was placed on it with the decorative plastic sheet facing down. Then, 4 weights of 250 g were placed on each corner on the curved tempered glass, a total load of 1 kg was applied, and the length of the dent mark formed on the decorative plastic sheet was measured and evaluated.

<Shrinkage evaluation>

After UV irradiation, the depth of the adhesive layer contracted due to photocuring at the edge of the decorative glass panel and dug into it was observed through a microscope, and then the average depth was measured 5 times.

<Measurement of glass transition temperature change temperature of adhesive layer before and after photocuring>

The change in glass transition temperature was measured using DSC by sampling the adhesive before and after UV irradiation. Using TA instruments' DSC, the temperature was raised from -80 °C to 150 °C at a rate of 10 °C/min. After the first scan, the temperature was immediately changed to -80 °C. The sample was again heated to 200 °C at a rate of 5 °C/min for a second scan.

Preparation of thermosetting acrylic copolymer

production example One

In a 5-neck 2L reactor, 55 parts by weight of butyl acrylate (LG Chem), 15 parts by weight of methyl acrylate (LG Chem), 15 parts by weight of 2-hydroxyethyl acrylate (Nippon Catalyst), ethoxy ethoxyethyl acrylate ( Miwon Specialty) 10 parts by weight and 5 parts by weight of hydroxyethyl acrylamide (Kyojin, Japan) were added, and then 226 parts by weight of ethyl acetate was added. After maintaining 65 ℃ while replacing with nitrogen at room temperature for 1 hour, a total of 1,400 ppm of AIBN (2,2'-azo-bis-isobutyronitrile) was added in 5 divided portions in 1 hour units until the conversion rate was 98% or more. An acrylic thermosetting acrylic copolymer was prepared while maintaining a nitrogen atmosphere. The acrylic copolymer had a weight average molecular weight of about 1.08 million, a solid content of 30.5%, and a viscosity of 15,500 cPs at 25°C/spindle 63.

production example 2

In a 5-neck 2L reactor, 55 parts by weight of butyl acrylate (LG Chem), 15 parts by weight of methyl acrylate (LG Chem), 10 parts by weight of 2-hydroxyethyl acrylate (Nippon Catalyst), ethoxy ethoxy ethyl acrylate ( Miwon Specialty) 10 parts by weight, hydroxyethyl acrylamide (Kyojin, Japan) 10 parts by weight, and then 226 parts by weight of ethyl acetate were added. After maintaining 65 ℃ while replacing with nitrogen at room temperature for 1 hour, a total of 1,400 ppm of AIBN (2,2'-azo-bis-isobutyronitrile) was added in 5 divided portions in 1 hour units until the conversion rate was 98% or more. An acrylic thermosetting acrylic copolymer was prepared while maintaining a nitrogen atmosphere. The acrylic copolymer had a weight average molecular weight of about 530,000, a solid content of 30.1%, and a viscosity of 2,500 cPs at 25°C/spindle 63.

3 sensuality Woori Tan acryl amide Preparation of oligomers

production example 3

In a 5-neck 3L reactor, 500 g of ethyl acetate for viscosity control and 277 g of oligomeric aliphatic polyisocyanate (T1890-100, Evonik, IPDI trimer) were added and stirred at 50° C. for 2 hours or more to dissolve all of T1890-100.

Then, 223 g of hydroxyethyl acrylamide (HEAA) (Kohjin) and 1.0 g of Irganox #1010 of BASF were sequentially added. While maintaining the temperature at 50 °C, 50 ppm of DBTDL (dibutyltin dilaurate) was dividedly added to induce an exothermic reaction, and the reaction was carried out while maintaining the temperature at 70 °C. After performing the reaction at the same temperature for 8 hours (confirming that the NCO peak disappeared at 2250 cm ^-1 on FT-IR), the temperature was lowered to 30° C. and then filtered through 200 mesh, IPDI in which R1 is H in Formula 1 An oligomer of trimer-(HEAA)3 was prepared. The oligomer had a weight average molecular weight on GPC of 1,250 g/mol and a PDI of 1.22. The viscosity was 910 cPs when measured with a Brook field LVII at 25° C./spindle No. 40, and the solid content was 50%.

production example 4

An oligomer of Formula 2 was prepared in the same manner as in Preparation Example 3 except that hydroxyethyl methacrylate (HEMA) was used instead of hydroxyethyl acrylamide (HEAA) (Kohjin). Oligomers were prepared.

The weight average molecular weight of this oligomer was 1,380 g/mol, and the PDI was 1.27. The viscosity was 750 cPs.

Example One

100 parts by weight of the thermosetting acrylic copolymer of Preparation Example 1, 7 parts by weight of the oligomer of Preparation Example 3, 5 parts by weight of Aronix M-140 (Toagosei), 40 parts by weight of ethyl acetate, 0.5 parts by weight of Irgacure 651 (Basf), and KBM403 (Shin-Etsu Corporation) 0.5 parts by weight was mixed to prepare a pressure-sensitive adhesive composition.

Example 2

100 parts by weight of the thermosetting acrylic copolymer of Preparation Example 2, 15 parts by weight of the oligomer of Preparation Example 3, 5 parts by weight of Aronix M-140 (Toagosei), 15 parts by weight of ethyl acetate, 0.5 parts by weight of Irgacure 651 (Basf), and KBM403 (Shin-Etsu Corporation) 0.5 parts by weight was mixed to prepare a pressure-sensitive adhesive composition.

Example 3

100 parts by weight of the thermosetting acrylic copolymer of Preparation Example 1, 7 parts by weight of the oligomer of Preparation Example 4, 5 parts by weight of Aronix M-140 (Toagosei), 45 parts by weight of ethyl acetate, 0.5 parts by weight of Irgacure 651 (Basf), and KBM403 (Shin-Etsu Corporation) 0.5 parts by weight was mixed to prepare a pressure-sensitive adhesive composition.

Example 4

100 parts by weight of the thermosetting acrylic copolymer of Preparation Example 2, 15 parts by weight of the oligomer of Preparation Example 4, 5 parts by weight of Aronix M-140 (Toagosei), 25 parts by weight of ethyl acetate, 0.5 parts by weight of Irgacure 651 (Basf), and KBM403 (Shin-Etsu Corporation) 0.5 parts by weight was mixed to prepare a pressure-sensitive adhesive composition.

comparative example One

100 parts by weight of the thermosetting acrylic copolymer of Preparation Example 1, 7 parts by weight of trimethylol propane triacrylate (Miwon Specialty, TMPTA) which is a trifunctional acrylate, 5 parts by weight of Aronix M-140 (Toagosei), 40 parts by weight of ethyl acetate A pressure-sensitive adhesive composition was prepared by mixing 0.5 parts by weight of Irgacure 651 (Basf) and 0.5 parts by weight of KBM403 (Shin-Etsu).

comparative example 2

100 parts by weight of the thermosetting acrylic copolymer of Preparation Example 2, 15 parts by weight of trimethylol propane triacrylate (Miwon Specialty, TMPTA) which is a trifunctional acrylate, 5 parts by weight of Aronix M-140 (Toagosei), 40 parts by weight of ethyl acetate A pressure-sensitive adhesive composition was prepared by mixing 0.5 parts by weight of Irgacure 651 (Basf) and 0.5 parts by weight of KBM403 (Shin-Etsu).

The pressure-sensitive adhesive compositions of Examples and Comparative Examples prepared by the above-described method were applied to a PET film and then thermosetted at 110° C. for 3 minutes to prepare a pressure-sensitive adhesive sheet composed of a layer having a thickness of 22 μm, respectively. Then, the prepared pressure-sensitive adhesive sheet was transferred to a decorative sheet made of PVC with a thickness of 100 μm, and then adhered to a curved tempered glass having a thickness of 5,000 μm as shown in reference numeral 30 in FIG. 1 . Various physical properties of the pressure-sensitive adhesive were evaluated according to the above-described method and shown in Table 1 below. In Table 1, UV irradiation was irradiated at 1,000 mJ/cm ² using a metal lamp.

Steps before UV irradiation Steps after UV irradiation characteristic Rework characteristics
(within 30 minutes) 30 minutes after Lami 4hr time elapsed after Lami side lift
Whether Storage Modulus
(25℃)/Pa degree of pressure after UV irradiation shrinkage evaluation UV irradiation
before → after
Tg change evaluation residue
(Residue)
Whether Adhesion evaluation
(kgf/in) Adhesion evaluation
(kgf/in) punch level
Adhesion evaluation
(kgf/in) If more than 2mm occurs, it is judged as NG. Tg temperature increase (°C) Example 1 Good 0.42kgf 1.4kgf Great 9.02 x 10 ⁵ 0.24mm 3.9kgf/in <<1mm 60.49 Example 2 Good 0.39kgf 1.34kgf Great 12.3 x 10 ⁵ 0.19mm 4.2kgf/in doesn't exist 80.49 Example 3 Good 0.51kgf 1.2kgf Great 6.02 x 10 ⁵ 0.28mm 3.2kgf/in <<1mm 55.0 Example 4 Good 0.53kgf 1.5kgf Great 7.02 x 10 ⁵ 0.22mm 3.1kgf/in <<1mm 71.2 Comparative Example 1 Good 0.51kgf 1.2kgf Inadequate 2.21 x 10 ⁵ 0.96mm 0.9kgf/in more than 2mm
NG 15 Comparative Example 2 Residue generation 0.53kgf 0.91kgf Inadequate 1.65 x 10 ⁵ 0.98mm 0.3kgf/in more than 3mm
NG 27.2

Referring to the results of Table 1, the pressure-sensitive adhesive according to the present invention has good rework properties and exhibits an appropriate adhesive strength prior to photocuring. In addition, unlike the comparative example, the side lifting phenomenon is improved and the compression resistance is good. After photocuring, the glass transition temperature rises significantly, and shrinkage hardly occurs despite excellent adhesion.

10: decorative plastic sheet
20: adhesive sheet
30: curved glass panel
40: adhesive layer
100: decorative glass panel

Claims (13)

Thermosetting comprising a polymer unit made of alkyl (meth)acrylate, polymer unit made of hydroxy (meth) acrylate, polymer unit made of alkoxy (meth) acrylate, and polymer unit made of hydroxyalkyl (meth) acrylamide acrylic copolymer ; and
It contains a photocurable urethane acrylic oligomer having 3 to 6 photoreactive functional groups,
The content of the polymer unit made of alkyl (meth) acrylate, polymer unit made of hydroxy (meth) acrylate, polymer unit made of alkoxy (meth) acrylate, and polymer unit made of hydroxyalkyl (meth) acrylamide is 50 to 80% by weight, 5 to 20% by weight, 5 to 20% by weight, and 2 to 20% by weight of the acrylic pressure-sensitive adhesive composition, respectively, based on the total polymerized units constituting the copolymer. The method of claim 1,
Based on 100 parts by weight of solid content,
The content of the thermosetting acrylic copolymer is 55 to 85 parts by weight,
The acrylic pressure-sensitive adhesive composition, characterized in that the content of the photocurable urethane acrylic oligomer is 5 to 25 parts by weight. The method of claim 1,
The weight ratio of the thermosetting acrylic copolymer and the photocurable urethane acrylic oligomer is 3:1 to 9:1. delete According to claim 1,
The polymerization unit made of the alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylic rate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and at least one selected from the group consisting of tetradecyl (meth) acrylate, hydroxy The polymerization unit made of (meth)acrylate is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate ) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate At least one selected from the group consisting of, the alkoxy (meth) acrylate polymerization unit is ethoxy ethoxy ethyl (meth) acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate and methoxy polyethylene glycol at least one selected from the group consisting of acrylates, and the hydroxyalkyl (meth)acrylamide is hydroxyethyl (meth)acrylamide, hydroxymethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide and An acrylic pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of hydroxybutyl (meth) acrylamide. The method of claim 1,
The polymerization unit made of the alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylic rate and at least two or more selected from the group consisting of t-butyl (meth) acrylate and sec-butyl (meth) acrylate, and the polymerization unit made of the hydroxy (meth) acrylate is 2-hydroxyethyl (meth) ) acrylate, the polymerization unit of the alkoxy (meth)acrylate is ethoxyethoxyethyl (meth)acrylate, and the hydroxyalkyl (meth)acrylamide is hydroxyethyl (meth)acrylamide. An acrylic pressure-sensitive adhesive composition comprising The method of claim 1,
The weight average molecular weight of the photocurable urethane acrylic oligomer is an acrylic pressure-sensitive adhesive composition, characterized in that 500 to 3,000 g / mol. According to claim 1,
The photocurable urethane acrylic oligomer is an acrylic pressure-sensitive adhesive composition, characterized in that derived from the reaction of an isocyanate-based compound and hydroxyalkyl (meth) acrylamide. The method of claim 1,
The photocurable urethane acrylic oligomer is an acrylic pressure-sensitive adhesive composition, characterized in that the compound represented by the following formula (1), a compound represented by the following formula (2), or a mixture thereof:
<Formula 1>

In Formula 1, R ₁ is hydrogen or a methyl group.
<Formula 2>

[Claim 10] An acrylic pressure-sensitive adhesive made of a thermosetting product of the acrylic pressure-sensitive adhesive composition according to any one of claims 1 to 3 and 5 to 9. 11. The method of claim 10,
The adhesive strength of the acrylic adhesive is 0.3 to 1.7 Kgf/in with respect to tempered glass at room temperature. 11. The acrylic pressure-sensitive adhesive according to claim 10, wherein the glass transition temperature after photocuring is increased by 60 to 100 °C compared to the glass transition temperature before photocuring of the acrylic pressure sensitive adhesive. A decorative glass panel comprising a decorative plastic sheet, a glass panel, and an adhesive layer interposed therebetween, comprising:
The adhesive layer is a decorative glass panel, characterized in that the photocured of the acrylic pressure-sensitive adhesive of claim 10.

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