KR20160108134A - UV Composition And Method for Laminating Bullet-Proof Panel Using The Same - Google Patents

Abstract

The present invention relates to a novel UV adhesive composition suitable for bonding acrylic and polycarbonate, and a method for bonding a bullet-proof panel using the same and, more specifically, to an UV adhesive composition and a method for bonding a bullet-proof panel using the same. The method for bonding a bullet-proof panel comprises: an UV adhesive outflow blocking step for installing an outflow preventing device on an edge or a side of polycarbonate or acrylic; an adhesive injection step; and a bonding step.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a UV adhesive composition and a method of bonding a bulletproof panel using the UV adhesive composition.

The present invention relates to a method for producing a new UV adhesive composition used for bonding polycarbonate (hereinafter referred to as 'PC') and acrylic, and a method for producing a bulletproof panel using the same. So that sufficient adhesion can be obtained even when a plurality of PCs and acryl are laminated.

The greatest requirement for bullet-proof panels is bulletproof performance. To date, much of the effort to improve the bulletproof performance of bullet-proof panels has resulted in the construction of glass + PCs or more than one glass and more than one PC Has been concentrated on the bulletproof panel joining of a laminated structure.

PC is a shock-resistant and transparent material with a specific gravity of only about 1/2 of that of glass, but has a higher impact energy absorption capacity, so that the total thickness of glass + PC is made thinner than the total thickness of glass + glass The impact resistance of the bullet-proof panel can be greatly improved and the secondary damage (damage to the inside of the bullet-proof panel due to the rear rupture or spalling of the base material even if the bullet is not penetrated) Do not. Accordingly, when the glass panel structure of the glass + PC structure is formed, the bulletproof performance is further improved as compared with the bulletproof panel made of glass or film, while the thickness is thin, the weight is light, the light transmittance is more excellent, A bulletproof panel can be manufactured.

However, in general, a glass-plus-glass bulletproof panel is disposed on the outside of the glass part and on the inside (inside or inside the building or on the vehicle) of the PC part so that when a bullet is fired on the bulletproof panel, The PC can defend, but scattered glass fragments around the bulletproof panel can cause damage to human life or property. Therefore, the bulletproof panel of the glass + PC structure can cause damage to the friend or co-worker due to the glass fragments emitted from the bulletproof panel of the peer in a situation where a large number of people perform joint operations, There is a problem that the damage may occur to the unspecified persons around the place.

Patent No. 10-1258388 discloses a patent for a bulletproof panel of a glass + PC structure, but this patent does not consider the damage caused by the fragments of the glass part. In addition, as a recent technology related to a bulletproof panel of glass + PC structure, Korean Patent No. 10-1585774, Korean Patent Application No. 10-2015-0179238, and Korean Patent Application 10-2014-0117622]. The first and second applications were to pre-treat the surface of the PC before bonding the glass to the PC to compensate for the weak chemical resistance of the PC, and developed a new UV adhesive to laminate multiple PCs. The third application omits the preprocessing process by developing a new UV adhesive that does not erode the surface of the PC, and originally solved the problem of sticking of dust or dirt to the surface of the PC which had been pretreated in the former application. These two applications, however, did not provide a solution to the problem that the fragments of glass fragments caused by shooting were radiated to people or objects around them.

However, the damage caused by the fragments of glass can occur at any time in the situation where a large number of people face joint firearms, and can occur at any time, especially in the police forces of countries that have to face counterterrorism forces or protesters carrying firearms. have.

This means that bulletproof panels are not enough to keep individual safety and that thorough consideration should be given to the bulletproof panel from the design and development stage so as not to damage the safety of both myself and my colleagues. It means that a bulletproof panel using a new base material that does not emit debris around it needs to be implemented.

Another problem that must be solved in a bulletproof panel using a PC is that it is necessary to laminate a plurality of PCs in multiple layers in order to realize a high level of bulletproof performance (refer to FIG. 5), but the ultraviolet transmittance of the PC is very low Therefore, it is not possible to properly bond bulletproof panels in which a plurality of PCs are stacked with conventional UV adhesive. [Korean Pat. No. 10-1038032] and [Korean Patent No. 10-1258388] described above all have a structure in which a plurality of PCs can be stacked. However, since a general UV adhesive is used, I can not get it.

On the other hand, Korean Patent No. 10-1585774, Korean Patent Application No. 10-2015-0179238, and Korean Patent Application No. 10-2014-0117622 filed by the applicants of the present invention also solve such problems The present application has developed a UV adhesive composition for bonding a glass and a PC, and since the present application has replaced glass with another substrate (acrylic), the present invention provides a new UV adhesive composition It has been necessary to newly develop a UV adhesive suitable for the substrate.

In the case of a bullet-proof panel using glass, there is a problem that the fragments generated in the glass portion are radiated to people or objects in the vicinity, causing damage, and as a result, when a large number of people perform an operation against the bullets jointly, May be unintentional damage to a peer around the bulletproof panel even though it is safe. The case of such damage is a global problem in the police forces of countries that have to face counterterrorism forces or protesters carrying firearms, and an essential solution is needed.

According to the present invention, the problem that the debris generated in the glass portion on the front of the bulletproof panel is radiated to people and objects around the bulletproof panel and causes damage to the bulletproof panel is solved at its source, thereby securing the safety of the user, The present invention aims to provide a manufacturing method of a bulletproof panel which does not pose a threat to the safety of the bulletproof panel.

In the present invention, by replacing the glass used in the conventional bulletproof panel with acryl, a bulletproof panel of an acrylic + PC structure is manufactured instead of a glass + PC structure, so that fragments generated in the glass portion at the time of shooting are radiated to nearby persons or objects I have solved the problem that caused the damage.

Unlike glass, acrylic does not generate fine debris at the time of shooting, and when a sufficient thickness of acrylic is used, it has a relatively large scale cracking property. Even when acrylic is cracked, large pieces of cracks, The acrylic can be a safe substrate that can replace glass. Further, since the specific gravity of acrylic is only half of that of the glass, the weight of the bulletproof panel can be expected to be further reduced, thereby reducing the load imposed on bulletproof vehicles and buildings. Particularly, the life of the vehicle can be increased by reducing the load of the bulletproof vehicle, the fuel cost can be reduced, and the portability of the bulletproof panel can be greatly improved.

The UV adhesive used in the PC + acrylic bonding in the present invention can be obtained by a method disclosed in Korean Patent No. 10-1585774 filed by the present applicants, Korean Patent Application No. 10-2015-0179238, 10-2014-0117622] and the like have to be newly developed in accordance with the properties of acrylic and PC because the characteristics of the substrate to be bonded are different. Most of the UV adhesives do not erode the glass, but the PC and the acrylic are eroded, and the components that erode the PC and the components that erode the acryl are also different from each other. Therefore, in the present invention, A new UV adhesive has been developed.

As described above, in the present invention, (1) acryl is used instead of glass as a base material for a bulletproof panel, and (2) a new UV adhesive suitable for bonding acryl and PC is developed.

In addition, in developing new UV adhesives, (1) PC and acrylic are poor chemically resistant substrates. Therefore, except for the components that erode the surface of PC or acrylic among the main constituents of general UV adhesive, (2) a photoinitiator having a main absorption wavelength region of a long wavelength band of 360 nm or longer is added to the above-mentioned new UV adhesive in order to be applied to a case where a plurality of PCs or acryls are laminated, 3) In response to the UV adhesive added to the long wavelength band, the lamp of the UV irradiation device was replaced with a lamp having a strong energy intensity at a long wavelength band with a high ultraviolet transmittance of PC and acrylic, thereby bonding the acrylic and the PC.

For reference, conventional UV adhesives are not specialized to be suitable for bonding of PC and acrylic, and most of them are made to react in a short wavelength band where ultraviolet transmittance of PC and acrylic is extremely low. In addition, PCs and acryl as pure base materials fail to block ultraviolet rays and are damaged by ultraviolet rays to cause yellowing, whitening, internal cracks, etc. In order to overcome such problems, most PCs currently on the market And acrylic are manufactured by blending the ultraviolet ray blocking component in the manufacturing stage. Therefore, PC and acrylic which are actually circulated have a high ultraviolet ray blocking rate, and therefore, when using a conventional UV glue which reacts mainly with ultraviolet rays of a short wavelength band, Can not be obtained.

The effects of the present invention are as follows.

First, by replacing the glass with acryl, the damage around the bulletproof panel due to the emission of the glass fragments was fundamentally prevented,

Secondly, it is possible to prevent damage to people and property as well as the surrounding people, thereby making it possible to manufacture safer bulletproof panels,

Third, the weight of the bulletproof panel can be greatly reduced by using PC and acrylic, which have a specific gravity half the level of glass, thereby greatly reducing the load burden on the building and the vehicle, thereby improving the durability of the vehicle and the building, And the portability of the bulletproof panel can be increased.

Fourth, by developing a new UV adhesive capable of ensuring excellent adhesion even when a plurality of PCs or acryl layers are laminated, it is possible to manufacture a bulletproof panel having safer and superior bulletproof performance,

Fifth, we have developed a new UV adhesive that does not erode the surface of PC or acrylic except the component that erodes the surface of PC or acrylic among the components of UV adhesive, so that cracks and haze caused by erosion after bonding To improve durability and visibility of bulletproof panels.

Figure 1 is a representative figure of [Korean Patent No. 10-1038032]
The second figure is representative of [Korean Patent No. 10-1258388]
Figure 3 is a representative view of the present invention
Fig. 4 shows an example in which an outflow preventing device for preventing leakage of the UV adhesive is installed
Figure 5 shows an example where two or more PCs or acrylics are used.

In describing the present invention, all terms including technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and unless the context clearly dictates otherwise , Nor is it interpreted in an ideal or overly formal sense.

As described above, in the present invention, (1) acrylic was used instead of glass used in the conventional bulletproof panel, and (2) a new UV adhesive suitable for bonding acrylic and PC was developed.

In developing new UV adhesives, (1) since PC and acrylic are poor chemical resistance, the surface of PC or acrylic, except the monomers that erode the surface of PC or acrylic among the main constituents of general UV adhesive, (2) In order to obtain a sufficient adhesive force even when a plurality of PCs or acryls are laminated, ultraviolet rays of a long wavelength of 360 nm or more, which has a relatively high ultraviolet transmittance of PC and acrylic, (3) replacing the lamp of the UV irradiation device with a UV lamp having a strong energy intensity from a long wavelength band having a high ultraviolet transmittance of PC and acrylic in accordance with the UV adhesive having the photoinitiator of the long wavelength band added thereto And acrylic and PC were bonded.

In addition, when manufacturing such a bulletproof panel by applying these solutions, a UV adhesive outflow blocking step of installing an outflow preventing device on the edge or side of the PC or acrylic to prevent the UV adhesive from flowing down; A photoinitiator component having a long wavelength range of 360 nm or longer as a main absorption wavelength region is added and a UV adhesive formed only of monomers that do not erode PC or acrylic except for the monomer which erodes the surface of PC or acrylic is applied on the joint surface of PC and acrylic An injecting step of injecting an adhesive; A bonding step of irradiating ultraviolet rays by placing a PC and acryl injected with an adhesive into a UV irradiation device; And so on.

In another embodiment of the present invention according to the experimental result that PC or acryl is not eroded even when the UV absorber is used within 15% by weight of the UV adhesive composition of the present invention, A UV adhesive outflow blocking step of installing an outflow preventing device on the edge or side of acrylic or acrylic; An adhesive injection step of injecting a UV adhesive containing 15% by weight or less of monomers eroding the surface of PC or acrylic into a bonding surface of PC and acrylic by adding a photoinitiator component having a long wavelength band of 360 nm or longer as a main absorption wavelength region; A bonding step of irradiating ultraviolet rays by placing a PC and acryl injected with an adhesive into a UV irradiation device; And so on.

The details of the present invention will be described with reference to FIG.

In the UV adhesive outflow blocking step, which is the first step of the present invention, an outflow preventing device is installed on the edge of the PC or acrylic to prevent the UV adhesive from flowing off the edge of the substrates to be bonded such as PC or acrylic. A preferred example of such an outflow preventing device is a double-sided tape such as an acrylic foam tape. In the case where the outflow preventing device is a double-sided tape, a preferable thickness is about 0.5 mm to 2 mm, and a preferable width is about 0.5 cm to 1 cm.

In the case where the leakage preventing device is not provided or the leakage preventing device is poor and the UV adhesive flows down, various problems arise. (1) If the UV adhesive flows down and the amount of the adhesive is insufficient, the adhesive is not evenly injected (2) Unevenly injected UV adhesive can cause imbalance in bulletproof performance (3) Waste of UV adhesive as much as it flows down (4) the troubles of wiping off the UV adhesive which flows down, and (5) in the case of the UV adhesive which erodes the substrate, the UV adhesive may erode the surface of the substrate during the wiping process to cause cracking or haze .

In order to prevent such a problem, as shown in FIG. 4 (a), after the outflow preventing device is installed on at least one of the rims of the PC, acrylic, and the like, It is preferable to additionally provide a prevention device.

In the second step of the present invention, a photoinitiator component having a long wavelength range of 360 nm or longer as a main absorption wavelength region is added and a new UV adhesive using only monomers that do not erode the surface of PC or acrylic is added to the joint surface of PC and acrylic . The purpose of adding (1) a photoinitiator component having a main absorption wavelength region of a long wavelength band of 360 nm or longer is to add a plurality of PCs and acrylates by utilizing the characteristics of PC and acrylic, which have a significantly high ultraviolet transmittance in a long wavelength band of 360 nm or longer In order to obtain a sufficient adhesive strength even in a bullet-proof panel, (2) the monomer component which erodes the surface of the PC or acrylic is excluded, thereby preventing the UV adhesive from eroding the substrates of the anti- (Coating or the like) to compensate for the chemical resistance of the acrylic resin, and to provide a more efficient bonding method of the bulletproof panel. This will be described in more detail below.

The ultraviolet transmittance of PC may vary depending on the PC thickness and the product, but it is generally about 0% in the short wavelength band (UVA) and 40 ~ 60% in the long wavelength band (UVV) And acrylic has a UV transmittance of 70 to 80% in a long wavelength band, though the ultraviolet transmittance is small in a short wavelength band (see Table 1). The transmittance in Table 1 is calculated as 100 in the case of no material , PC is the data of Makrolon which is the product of Bayer, which is the number one PC market share in Korea, and acrylic is the data of the third place in Acrylic market in Korea. In addition, mercury lamps show high transmittance at long wavelength, but they are less than 60% of gallium lamp in terms of light intensity (UVV standard). Therefore, they have strong energy intensity at long wavelengths such as gallium lamp, metal lamp, fusion lamp and UV LED lamp. Is more preferable. Accordingly, in order to obtain a sufficient adhesive force even in a bulletproof panel in which a plurality of PCs and acryl are laminated, a UV adhesive which can be used in a long wavelength band having a high ultraviolet transmittance of PC and acrylic is developed, It is preferable to use a lamp having a strong energy intensity in the case of a lamp.

No Material PC (5T) PC (10T) Acrylic (5T) Acrylic (10T) lamp Hg Ga Hg Ga Hg Ga Hg Ga Hg Ga wavelength UVA UVV UVA UVV UVA UVV UVA UVV UVA UVV UVA UVV UVA UVV UVA UVV UVA UVV UVA UVV Light quantity mj / ㎠ 380 353 450 602 One 215 One 376 0 145 0 244 9 311 12 522 0 270 0 472 Transmittance (%) 100 100 100 100 0.3 61 0.3 63 0 41 0 41 2.4 88 2.7 87 0 77 0 78

In view of this point, in the present invention, a new UV adhesive composition has been developed in which a photoinitiator having a long wavelength band of 360 nm or longer as a main absorption wavelength region is added so that sufficient adhesion can be obtained even when a plurality of PCs or acryl layers are laminated.

The UV adhesive composition developed in the present invention will be described in detail.

The UV adhesive composition of the present invention is used as a mixture of at least one of urethane (meth) acrylate, epoxy acrylate, polyester acrylate, unsaturated polyester and acryl acrylate as an oligomer. Although urethane (meth) acrylate is soft and has good adhesion and impact resistance, it has a problem that the tensile force of the bonding layer is great and cracks easily due to external pressure or impact. Epoxy acrylate has excellent adhesion and chemical / mechanical properties, And the impact resistance is low. Polyester acrylate and unsaturated polyester have excellent workability, but have poor adhesion and impact resistance. Acrylic acrylate has good adhesion, but low impact resistance and heat resistance. Therefore, the UV adhesive composition of the present invention can be obtained by mixing at least one of the above urethane (meth) acrylate, epoxy acrylate, polyester acrylate, unsaturated polyester and acryl acrylate, and adding a (meth) acrylate monomer By using the mixture, the disadvantages of the oligomer were compensated and the advantage was maximized.

Here, the oligomer may be used in an amount of 20 to 60% by weight based on the total weight of the UV adhesive composition. If the amount of the oligomer is more than 60% by weight, the viscosity of the composition becomes too high, the tensile force is reduced, and the impact resistance becomes poor. When the amount is less than 20% by weight,

Examples of the monomer included in the UV adhesive composition of the present invention include glycerol propylate triacrylate, dicyclopentyl acrylate, ditrimethylol propane tetraacrylate, dipropylene glycol diacrylate, bisphenol acrylate, 3 ethoxydiacrylate, bisphenol 4 ethoxydiacrylate, isooctyl acrylate, ethylhexyl acrylate, octyldecyl acrylate, isobornyl acrylate, carboxyethyl acrylate, trimethylol propane ethoxy triacrylate, tri But are not limited to, methylol propane triacrylate, tripropylene glycol diacrylate, trioleoethyl methacrylate, pentaerythritol triacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol monoacrylate, 0.0 > neopentylglycoldi < / RTI > acrylate , Hydroxyphenoxypropyl acrylate, hydroxypropylmethacrylate, hydroxypivalic execte neopentylglycoldiacrylate, or a mixture thereof, and the multifunctional monomer includes 1,6-hexanediol di ( Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethanol diacrylate, tripropylene glycol di Acrylate, and pentaerythritol tri (meth) acrylate may be used.

On the other hand, among the monomers commonly used in common UV adhesives, those that erode the surface of PC include novinyl pyrrolidone, dimethylacetoacetamide, diethylene glycol dimethyl methacrylate, methyl methacrylate, butanediol diacrylate, cyclo Hexyl methacrylate, styrene monomer, acryloylmorpholine, ethoxyethoxyethyl acrylate, ethylene glycol dimethyl methacrylate, tetrahydroperfuryl acrylate, hexanediol diacrylate and the like, and hydroxyethyl methacrylate It is not preferable to use acrylate, phenoxyethyl acrylate, caprolactone acrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and the like.

However, in the case where monomers eroding the PC or acrylic are inevitably used, the amount thereof is limited to 15% by weight or less based on the total weight of the UV adhesive composition, and after the UV adhesive is injected, It was confirmed through experimentation that erosion did not occur on the surface of the PC or acrylic (see Example 2 and Example 3)

In this case, the criterion for judging whether or not a specific monomer erodes the PC or acrylic is the total time required for bonding the PC and acrylic to the UV adhesive (UV adhesive injection time + time to move to the UV irradiation device + (The sum of the time required for curing with a lamp), and whether or not the monomer erodes the surface of the PC or acrylic to cause cracks or haze during a period of about 30 minutes which is sufficiently long The haze phenomenon occurs mainly, and when the acrylic is eroded, the haze is insignificant but the crack is prominently generated.) In view of this, also in the case of the monomer eroding the PC or acrylic, the weight of the UV adhesive composition of the present invention is 15 weight %, It can be said that it does not deviate from the purpose or purpose of the present application.

The monomer may comprise from 30 to 79.8% by weight, based on the total weight of the UV adhesive composition. If the monomer content is more than 79.8% by weight, the strength of the cured coating film becomes too low, and the curing degree is lowered to deteriorate the heat resistance. If the monomer content is less than 30% by weight, the adhesion is poor.

The UV adhesive composition of the present invention comprises a photoinitiator having a main absorption wavelength region of ultraviolet light having a wavelength of longer than 360 nm. Such photoinitiators include (1-6-eta-cumene) (? -Cyclopentadienyl) iron (1+) hexafluorophosphate (1-), 1- 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, (4-methylthiophenyl) -2- (4-morpholinyl) -1-propanone, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-chlorothioxanthone, 3-methylacetophenone, 4,4'-dimethoxybenzophenone, Benzoin ethyl ether, benzoin propyl ether, benzophenone, benzaldehyde, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, anthraquinone, isopropyl thioxane Santon, camphorquinone, thioxanthone, etc., and one of these photoinitiators may be used alone Used or may be used by mixing two or more. It may also be used in combination with a photoinitiator that reacts at a short wavelength band.

The photoinitiator may include 0.1 to 10% by weight based on the total weight of the UV adhesive composition. If the amount of the photoinitiator is less than 0.1% by weight, the curability is deteriorated to deteriorate the productivity. If the amount is more than 10% by weight, the cost increases and the amount of other components decreases.

The UV adhesive composition of the present invention may further contain 0.1 to 5% by weight of an additive such as a silane coupling agent, phosphorus ester acrylate, thermal polymerization inhibitor, smoothing agent, surfactant, antifoaming agent, etc., based on the total weight.

Thus, in the present invention, 20 to 60% by weight of an oligomer, 30 to 79.8% by weight of a monomer that does not corrode PC or acrylic, 0.1 to 10% by weight of a photoinitiator having a long wavelength range of 360 nm or longer as a main absorption wavelength region, % And the like were mixed to prepare a UV adhesive composition. Further, in another embodiment of the present invention, in which a PC or an acrylic-eroding monomer is used within a threshold value (15 wt%), 20 to 60 wt% of an oligomer, 0 to 15 wt% of a PC or an acrylic- A photoinitiator having a main absorption wavelength range of 360 nm or longer, and 0.1 to 5 wt% of an additive were mixed to prepare a UV adhesive composition.

Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not limited by these examples without departing from the gist of the present invention.

10 wt% of a photoinitiator having ultraviolet light of a long wavelength band of 360 nm or longer as a main absorption wavelength region was mixed with 25 wt% of an oligomer, 20 wt% of hydroxypropyl (meth) acrylate, 40 wt% of isobonyl (meth) acrylate, A UV adhesive composition was prepared by mixing, and this composition was used for adhesion of one PC and one acrylic. In addition, ultraviolet rays were irradiated from the PC side using a UV irradiation device equipped with a fusion lamp (D-Bulb).

10 wt% of a photoinitiator having ultraviolet light of a long wavelength band of 360 nm or longer as a main absorption wavelength region was mixed with 25 wt% of an oligomer, 20 wt% of hydroxypropyl (meth) acrylate, 30 wt% of isobonyl (meth) acrylate, 10% by weight of an eroding monomer tetrahydrofurfuryl (meth) acrylate, 5% by weight of an additive, etc. to prepare a UV adhesive composition, which was used for adhesion of one PC and one acrylic. In addition, ultraviolet rays were irradiated from the PC side using a UV irradiation device equipped with a fusion lamp (D-Bulb).

10 wt% of a photoinitiator having ultraviolet light of a long wavelength band of 360 nm or longer as a main absorption wavelength region was mixed with 25 wt% of an oligomer, 20 wt% of hydroxypropyl (meth) acrylate, 30 wt% of isobonyl (meth) acrylate, 10% by weight of erodible monomer butanediol diacrylate, 5% by weight of additives, etc. to prepare a UV adhesive composition, which was used for adhesion of one PC and one acrylic. In addition, ultraviolet rays were irradiated from the PC side using a UV irradiation device equipped with a fusion lamp (D-Bulb).

[Comparative Example 1]

10% by weight of a photoinitiator having a main absorption wavelength range of a long wavelength band of 360 nm or longer as a main absorption spectrum, 25% by weight of an oligomer, 20% by weight of hydroxypropyl (meth) acrylate, monomer tetrahydrofurfuryl (meth) 40% by weight, 5% by weight of additives, etc., to prepare a UV adhesive composition, which was used for bonding one PC and one acrylic. In addition, ultraviolet rays were irradiated from the PC side using a UV irradiation device equipped with a fusion lamp (D-Bulb).

[Comparative Example 2]

10% by weight of a photoinitiator having a main absorption wavelength region of a long wavelength band of 360 nm or more as a main absorbing wavelength region, 25% by weight of oligomers, 20% by weight of hydroxypropyl (meth) acrylate, 40% by weight of monomer butanediol diacrylate eroding both PC and acryl, 5% by weight of additives, etc. to prepare a UV adhesive composition, which was used for bonding one PC and one acrylic. In addition, ultraviolet rays were irradiated from the PC side using a UV irradiation device equipped with a fusion lamp (D-Bulb).

[Comparative Example 3]

10 wt% of a photoinitiator having a long wavelength band of 360 nm or longer as a main absorption wavelength region, 25 wt% of an oligomer, 20 wt% of hydroxypropyl (meth) acrylate, 10 wt% of isobonyl (meth) 30% by weight of erodible monomer hexanediol diacrylate, 5% by weight of additives, etc. to prepare a UV adhesive composition, which was used for adhesion of one PC and one acrylic. In addition, ultraviolet rays were irradiated from the PC side using a UV irradiation device equipped with a UVA lamp.

The bulletproof panel bonded by the above-mentioned Examples 1, 2, 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3 was evaluated as to whether or not haze occurred, whether or not it was peeled off by impact, And whether or not the coating film was formed when ultraviolet rays were irradiated from the PC side and bonded.

The occurrence of haze was first measured by visual inspection before UV adhesive bonding, UV bonding after UV adhesive application, and second measurement after a total of 30 minutes from UV adhesive injection. The detachment due to the impact is determined by the impact of a bulletproof panel made of a thickness sufficient for an adult to break down with a hammer or hammer (one PC 5T and one acrylic 5T are joined) Whether or not the bonded surface was peeled off was judged (it is judged that the peeled peeled peeled peel off the peeled peeled peel). Whether or not the gun was peeled off was measured with a 38-gauge handgun equipped with a normal shot (bomb) and aimed at a distance of 5 meters. Then, whether or not the PC-acrylic interface was peeled off regardless of penetration of the bulletproof panel was measured. It is natural that the bulletproof panel peeled off by the impact is also peeled off by the shooting, but the impact test and the shooting experiment are performed for the sure verification. In all of the above Examples and Comparative Examples, ultraviolet rays were irradiated from the PC side. Whether or not sufficient adhesive force was obtained was judged as the same method as that of the impact by peeling (confirmation of peeling after peeling).

The results of these measurements are shown in Table 2 below.

Haze occurrence Detachment by impact Detachment by shooting Whether the coating film is formed at the time of irradiation from the PC side Example 1 × × × ○ Example 2 × × × ○ Example 3 × × × ○ Comparative Example 1 ○ × × ○ Comparative Example 2 ○ × × ○ Comparative Example 3 ○ ○ ○ ×

In Example 2, 10 wt% of tetrahydrofurfuryl (meth) acrylate, which is a monomer that erodes both PC and acryl, was used. In Example 3, 10 wt% of butanediol diacrylate, which is a monomer that erodes both PC and acryl, Respectively. As a result, even if monomers that erode PC or acryl are used within a threshold value (within 15 wt% of the total weight of the UV adhesive composition of the present invention), and haze is not generated .

On the other hand, in Comparative Example 1, 40% by weight of monomer tetrahydrofurfuryl (meth) acrylate which erodes both PC and acryl was used. In Comparative Example 2, 40% by weight of monomer butanediol diacrylate, which erodes both PC and acryl, In Comparative Example 3, 30% by weight of monomer hexane diol diacrylate, which also erodes PC, was used. Through this, it can be confirmed that haze occurs on the surface of the PC when the monomers eroding the PC are used above the threshold value. In Comparative Example 3, since a UVA lamp was mounted and ultraviolet rays were irradiated from the PC side, a sufficient coating film was not formed.

On the other hand, the preferred viscosity of the UV adhesive of the present invention is 5 to 2000 cps. If the viscosity is significantly lower than 5 cps, the UV adhesive may be injected at a high rate in the adhesive injection step and may flow out of the outflow prevention device. If the outflow preventing device is a double-sided tape, it may cause deformation on the double- When the curing temperature is higher than 2000 cps, it takes a long time to inject the UV adhesive, so that the working time is lengthened. In the meantime, some components of the UV adhesive can erode the substrate such as PC,

The appropriate thickness of the adhesive injected in the adhesive injection step is preferably similar to the height of the outflow preventing device such as the acrylic foam tape installed in the UV adhesive outflow blocking step of the previous step. If the amount of the UV adhesive is insufficient Air bubbles can be generated and eventually peeled off, which can cause a lethal problem in the life of the bulletproof panel.

Generally, the cause of bubbles is (1) the amount of injected UV adhesive is insufficient, (2) enough UV adhesive is injected but the UV adhesive is leaked out, and (3) And the case where air is introduced into the UV adhesive and the like. (1) can be solved by injecting a sufficient amount of adhesive, (2) can be solved by properly installing an outflow preventing device, (3) It can be solved by flowing together and injecting enough UV adhesive again.

The bonding step of the third step is a step of irradiating ultraviolet rays with a PC and acryl injected with an adhesive into a UV irradiator. In the present invention, an extension line of a UV absorber adding a photoinitiator having a main absorption wavelength range of 360 nm or longer wavelength ultraviolet , The lamp of the UV irradiation apparatus was replaced by a general UVA lamp or a mercury lamp with a lamp having a high energy intensity at a long wavelength band of 360 nm or longer. At present, examples of such lamps include a gallium lamp, a metal lamp, a D-Bulb, a V-Bulb, and a UV LED lamp, but the object of the present invention is not limited to this example. By replacing the lamp of the UV irradiating device as described above, ultraviolet rays of about 40% can be transmitted through a PC having a thickness of 10T, and thus sufficient adhesion can be obtained even when a plurality of PCs and acryl are laminated.

For reference, even in the case of a bulletproof panel in which a plurality of PCs or acryl layers are laminated, not all of the substrates are bonded together, but they are individually bonded in units of one bonding surface (for example, one acrylic and one PC) The ultraviolet transmittance does not gradually converge to 0 even if a plurality of PCs or acryls are stacked as shown in Figs. 5A and 5B, and the transmittance of about 40 to 60% as shown in Table 1 can be always maintained .

Thus, in the present invention, by (1) replacing glass with acryl, it is possible to prevent damage to the surroundings caused by glass fragments, and (2) to prevent damage to persons and property (3) By using PC and acrylic, which have a specific gravity of half the glass level, it is possible to reduce the weight of the bulletproof panel to less than half the level, (4) It is possible to improve the durability of vehicles and buildings, reduce the fuel cost of vehicles and increase the portability of bulletproof panels. (4) By developing a UV adhesive, it is possible to manufacture a bulletproof panel having safer and superior bulletproof performance. (5) The development of new UV adhesives made only of monomers that do not corrode the surface of PC or acrylic except the monomers which erode the surface of PC or acrylic in the mercury prevents cracks and haze caused by erosion after bonding, Durability and improved visibility.

(10) Front glass part (30) Outer nano ceramic film (31) Inner nano ceramic film (40) Polycarbonate (50) Outflow preventing device (60) Acrylic base layer (120)

Claims (6)

A UV adhesive outflow blocking step in which an outflow preventing device is provided on the edge or side of the polycarbonate or acrylic so that the UV adhesive does not flow down;
A photoinitiator component having a long wavelength range of 360 nm or longer as a main absorption wavelength region was added and a UV adhesive formed by using only monomers that did not erode polycarbonate and acrylic within 30 minutes as a monomer as a monomer as a reactive monomer was changed to polycarbonate And an acrylic adhesive;
And a bonding step of irradiating ultraviolet light by placing the polycarbonate and the acrylic into which the UV adhesive is injected into the UV irradiation device,
Monomers which do not corrode polycarbonate and acrylic within 30 minutes after the above application are glycerol propylate triacrylate, dicyclopentyl acrylate, ditrimethylol propane tetraacrylate, dipropylene glycol diacrylate, bisphenol 3 But are not limited to, ethoxydiacrylate, bisphenol 4 ethoxydiacrylate, isooctyl acrylate, ethylhexyl acrylate, octyldecyl acrylate, isobornyl acrylate, carboxyethyl acrylate, trimethylol propane ethoxy triacrylate, Triethylene glycol monoacrylate, triethylene glycol monoacrylate, propylene glycol monoacrylate, triethylene glycol monoacrylate, propylene glycol monoacrylate, triethylene glycol monoacrylate, Neopentylglycoldiacrylate Hydroxypropyl methacrylate, hydroxypivalic exe neopentyl glycol diacrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol diacrylate, tripropylene glycol diacrylate, pentaerythritol tri (meth) , Or a mixture of two or more thereof. 20 to 60% by weight of an oligomer obtained by mixing at least one of urethane (meth) acrylate, epoxy acrylate, polyester acrylate, unsaturated polyester and acrylic acrylate;
30 to 79.8% by weight of monomers which do not erode polycarbonate and acrylic within 30 minutes after application;
0.1 to 10% by weight of a photoinitiator having ultraviolet light of a long wavelength band of 360 nm or more as a main absorption wavelength region;
0.1 to 5% by weight of an additive,
A viscosity of from 5 cps to 2000 cps,
Monomers which do not corrode polycarbonate and acrylic within 30 minutes after the above application are glycerol propylate triacrylate, dicyclopentyl acrylate, ditrimethylol propane tetraacrylate, dipropylene glycol diacrylate, bisphenol 3 But are not limited to, ethoxydiacrylate, bisphenol 4 ethoxydiacrylate, isooctyl acrylate, ethylhexyl acrylate, octyldecyl acrylate, isobornyl acrylate, carboxyethyl acrylate, trimethylol propane ethoxy triacrylate, Triethylene glycol monoacrylate, triethylene glycol monoacrylate, propylene glycol monoacrylate, triethylene glycol monoacrylate, propylene glycol monoacrylate, triethylene glycol monoacrylate, Neopentylglycoldiacrylate Hydroxypropyl methacrylate, hydroxypivalic exe neopentyl glycol diacrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol diacrylate, tripropylene glycol diacrylate, pentaerythritol tri (meth) ≪ / RTI > or a mixture of two or more thereof. A UV adhesive outflow blocking step in which an outflow preventing device is provided on the edge or side of the polycarbonate or acrylic so that the UV adhesive does not flow down;
A photoinitiator component having a main absorption wavelength region of a long wavelength band of 360 nm or longer is added and a UV adhesive containing 15% by weight or less of polycarbonate or acrylic-eroding monomer is applied to the joint surface of the polycarbonate and acrylic within 30 minutes after application An adhesive injection step;
And a bonding step of irradiating ultraviolet light by placing the polycarbonate and the acrylic into which the UV adhesive is injected into the UV irradiation device,
Within 30 minutes after application, the polycarbonate or acrylic eroding monomer
N-butyl acrylate, n-butyl acrylate, n-butyl acrylate, n-butyl acrylate, n-butyl acrylate, n-butyl acrylate, Acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, ethylhexyl acrylate, ethylhexyl acrylate, ethylhexyl acrylate, And a hydroxypropyl acrylate, or a mixture of two or more thereof. 20 to 60% by weight of an oligomer obtained by mixing at least one of urethane (meth) acrylate, epoxy acrylate, polyester acrylate, unsaturated polyester and acrylic acrylate;
30 to 79.8% by weight of monomers which do not erode polycarbonate and acrylic within 30 minutes after application;
0 to 15% by weight of monomers that erode polycarbonate or acrylic within 30 minutes after application;
0.1 to 10% by weight of a photoinitiator having ultraviolet light of a long wavelength band of 360 nm or more as a main absorption wavelength region;
0.1 to 5% by weight of an additive,
A viscosity of from 5 cps to 2000 cps,
Monomers which do not corrode polycarbonate and acrylic within 30 minutes after the above application are glycerol propylate triacrylate, dicyclopentyl acrylate, ditrimethylol propane tetraacrylate, dipropylene glycol diacrylate, bisphenol 3 But are not limited to, ethoxydiacrylate, bisphenol 4 ethoxydiacrylate, isooctyl acrylate, ethylhexyl acrylate, octyldecyl acrylate, isobornyl acrylate, carboxyethyl acrylate, trimethylol propane ethoxy triacrylate, Triethylene glycol monoacrylate, triethylene glycol monoacrylate, propylene glycol monoacrylate, triethylene glycol monoacrylate, propylene glycol monoacrylate, triethylene glycol monoacrylate, Neopentylglycoldiacrylate Hydroxypropyl methacrylate, hydroxypivalic exe neopentyl glycol diacrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol diacrylate, tripropylene glycol diacrylate, pentaerythritol tri (meth) Or a mixture of two or more thereof
Within 30 minutes after the above application, the polycarbonate or acrylic eroding monomer may be selected from the group consisting of normal vinyl pyrrolidone, dimethylacetoacetamide, diethylene glycol diacrylate, methyl methacrylate, butanediol diacrylate, cyclohexyl methacrylate Acrylonitrile, acrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, , Caprolactone acrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, or a mixture of two or more thereof. The bulletproof panel joining method according to claim 1 or 3, wherein the lamp of the UV irradiation apparatus is one of a gallium lamp, a metal lamp, a fusion lamp, and a UV LED lamp The method according to claim 2 or 4, wherein the photoinitiator is a mixture of one or more photoinitiators whose main absorption wavelength region is ultraviolet light of a long wavelength band of 360 nm or more, one or more photoinitiators whose main absorption wavelength region is ultraviolet light of a long wavelength band of 360 nm or more, Lt; RTI ID = 0.0 > UV < / RTI >

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