JPS5918775A - Radiation-curable pressure-sensitive adhesive composition - Google Patents

Abstract

PURPOSE:To obtain titled composition of high adhesivity and cohesivity, by incorporating each specific amount of a chain transfer agent and an acidic group- contg. monomer in a radiation-curable liquid oligomer having radically crosslikable ethylenic unsaturated double bond. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 parts by wt. of a radiation-curable liquid oligomer having, in one molecule, radically crosslinkable ethylenic unsaturated double bond (pref. an acrylic oligomer with its unsaturated double bond present in the side chain or at the terminal, having a viscosity of 10<2>-10<5>cps at room temperature, e.g., a polyester acrylate), with (B) 0.2-20 parts of wt. of a chain transfer agent (e.g., lauryl mercaptan), and (C) 0.5-30 parts by wt. of an acidic group-contg. monomer (e.g., 2-acid phosphoxyethyl acrylate). When carrying out a radiation polymerization, it is recommended to apply an electron beam irradiation with a dose of 1- 20Mrad. EFFECT:Having excellent rubbery properties.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a radiation-curable pressure-sensitive adhesive composition with excellent crystalline cohesion and adhesion.

Conventionally, in pressure-sensitive viscous tags, the desired cohesive force,
In order to exhibit contact layer characteristics such as contact force l, a relatively high polymer material and a viscosity M combination (Tsuri, natural rubber, base rubber, etc.) are used.
It was necessary to use the sound mail. For this GIJ, the coating (during IJ, in an organic solvent) must be applied on the substrate as a bath #, and then the FD agent used in it must be evaporated. In order to prevent
71! All JJ is safe. Moreover, if it is used for soil dα purposes, it will rarely burn or burn due to its volatilization, and it will often cause negative effects on the human body, so its usage power 3 often causes fires. In addition, from the viewpoint of red skin and the above-mentioned pollution prevention viewpoint, the installation of bath salt collection equipment is unavoidable, and the island's general FC is expensive. In addition, a large proboscis is required in terms of equipment.In recent years, attention has been paid to the use of pressure-sensitive adhesives as bath agents, from the viewpoints of saving capital, energy, and eliminating pollution. ◇There are emulsion type, hot melt type, and other types of disinfectants that can be used as a solvent-free solution, but radiation-curable pressure-sensitive disinfectants that use hostile oligomers are particularly in the spotlight. The reason is radiation
1! lj! It is a curable pressure-sensitive layering agent that does not, in principle, contain the /fT solvent, which is a disadvantage of the bath liquid-type pressure-sensitive layering agent mentioned above, and can be made without a so-called TD agent.

Ai, even if it is 0 miya, a small amount will come out, and since it uses radiation r, which is an old energy ray, the curing (M unit) reaction is fast; (2) The curing fabric 6 is a radiation irradiation type. (6) Excluding manufacturing, people can rest assured that the pot line will harden or progress /), so the pot line can be adjusted freely. This is the 7th time.

On the other hand, even the radiation-curing pressure-sensitive groove contacting agent @8 has the following failure point. 19. Radiation #J for general VC base (curing) reaction! After irradiation, the pressure generated radical IL L 9 ,
Although it progresses to unsaturated 2M residues, the reaction rate is fast and excessive crosslinking is difficult. (As a result, the glass transition point rises.) Because of its IL, the formed film is brittle, and
A sharp feeling arises when Tsumugi is used. Examining the properties of the film in this state shows that it has a high breaking strength, but has little elongation and does not have rubber-like properties. On the other hand, excessive cross-linking? Because of the inhibition Go6, the absolute value of the intramolecular
Kasugo and 71/b have a light cohesive power.

As mentioned above, it is difficult to properly control the curing reaction and maintain all adhesive properties as a pressure-sensitive adhesive. −
Ah π0 Therefore, the inventors of the present invention filed a patent application in 1983- + 0
As shown in No. 667, a chain transfer agent of 65% was added and curing (
Burial) Gray land/All other places, uniform-VC
As it progresses, it is found that the scales give rubbery properties. In order to develop a pressure-sensitive layering agent with even higher cohesive force and layering properties, we conducted a series of in-depth research into a chain, V-agent V (some plump body). In order to achieve the purpose of warping, the entire set of monomers is assembled together and contains one formula.However, for the purpose of non-invention, a radiation-curable pressure-sensitive adhesive was developed. Ijyi Radical crosslinkable ethylenic vesicles first MWj
The objective is to allow the curing reaction to proceed as uniformly as possible, maintain a constant crosslinking density, and at the same time increase surface chipping. Therefore, the curing speed is kept constant by the chain transfer reaction by the transfer agent VC, and the aggregation between molecules is suppressed.
It is something that strengthens you.

In other words, in the present invention, radical cross-linkable ether/sex vesicles, IJ double bonds, and 41. The amount of chain transfer agent is 0.2 to 100 parts by weight of the radiation-curable liquid oligomer VC.
The present invention is a radiation-curable pressure-sensitive adhesive composition characterized by containing 20 M parts and 0.5 to 60 parts of a monomer having an acidic group.

It is essential to add a chain transfer agent to rJ in the uninvented composite bottom VC, but it is difficult to add 31. Butyl mercaptan, lauryl mercaptan, thioglycol, ethylene glycol ditheoglycolate, pentaerythritol tetrabase ÷ β-teoglobionate), diphenyldinol 2ide, di-sulfide, etc. carbon tetrachloride, carbon tetrabromide,
Chloroform, dichlorobenzene, etc., halogenated substances, etc. Cn et al. may be used with single J insects, or 17
You may mix and use t2tm or more. These 21 chain transfer agents are added with 2'L to completely suppress QJ excessive crosslinking during radiation curing.
So 5 sounds tlfrt'? r: o, 2-20 m%
Preferably a, 2 to 15% seedlings υ range 1 included in the selection 0. This fence is 0.2 % υ 4 to C, the effect of suppressing crosslinking is insufficient'''C : If the amount exceeds 20% by weight, curing will be insufficient, resulting in a lack of vigor and adversely affecting the quality of bamboo shoots.

On the other hand, acrylic acid is a monomer that contains hostile groups as an essential ingredient.

Methacrylic acid, itaconic acid, maleic acid, crotonic acid,
Acryloyloxyethyl + 2”-7
Acrylamide 2-methylgloban-sulfone, 5-
Chloro-2-7sido>lzpoki/globil methacrylate, 2-acynd phosphooxine ether acrylate, 2-and phosphooxine glovir methacrylate,
Phosphorus can be di(2-acryloyloxyether), phosphorus can be di(2-acryloyloxyenal), and so on. In particular, it's a good idea to put the eaves h□1 on the foot.
Select a monomer with a phosphoric acid group in the range of 0.5 to 60 quintillion 0.5 to 60 quintillion quintillion ``C'' to add these acidic groups.C. I have a child and 50Mth
If it exceeds IL%, the radiation curability and physical properties of the cured coating film (/, l) will deteriorate, making the housing unfavorable.

Radical linkage in the molecule, enalene, 1, 1, 2, 1, 2, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 4, 5, 4, 5, 4, 5, 4, 5, 5, 4, 5, 5, 5, 4, 5, 5, 4, 5, 5, , , , , , , , , ,, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and 10 , respectively, a radical linkage was introduced into the molecule. (Oligomer kil-IL combined with li), polyol acrylate, polynisdel acrylate, urethane acrylate,
Acrylic oligomers with 91 or more unsaturated nyl axes per molecule, such as epoxy acrylate, or VC side chains, and % polyptadiene/, polychlorogrene,
0.1 fc containing reactive preformates such as polyisogrene, sled oligomers are liquid, and are free of liquids, so even if you use a solvent, a small amount will come out. Furthermore, as the sticky armpit, it is 10 cps ~ 5 x 10' cps range v5
It is. It should be noted that in 2 cases of non-invention, the result is 2L Ruri 111 reactivity, and the acrylic yarn is 2 stops introduction 8.
There is an oligomer ``7'' which has been given with.

′! In addition, to this radiation fJJ hardened liquid oligomer, add softener, antioxidant, etc. to the viscous M agent 1' x D s history according to your peace of mind. There is a platform to do this. 0 In terms of non-invention, radiation and V'J, viscous energy rays include α rays, βL, γ, neutron rays, and acceleration. The field of 9°-separated radiation, which is used for ultraviolet radiation, can be used in the range of 0.5 to 50 Δ4 rad, preferably about 1 to 20 Mrad.

11 ultraviolet edge (1,) lifting platform, approximately 1t30 nm ~ 460
In the dry range of 100 nm, corrosion caused by mercury lamps, etc. may be cited as examples of corrosion.
ultraviolet? In the case of tlj, the irradiation atmosphere can be increased, and the irradiation atmosphere can also be increased. 1ν, the generated m radicals are inhibited by the I/J junction in the air, and in the case of 礪-8VL, they are immediately recovered by the inert residue, but the t on the film is
It may be coated with Neulum Shizuka.

The following is a one-shot reading. In addition, in the following, it is indicated if Dobekura.

Example 1, Comparative Example 1.2 Butyl acrylate 80 parts, glycidyl methacrylate 2
The existence of a melting medium - U is a JLV-shaped Taterai r, and the acrylic type of bath additives are both '6 bodies.

The liquid oligomer viscous material used by the samurai was 5XIO' centiboise (60°C). υ(In, acrylic acid 10
As a chain transfer agent, lauryl mel was added as a chain transfer agent to 100 parts of a radiation-curing liquid oligomer. Kaptafu 8 part, Shiki et al. K 7 V :/
Dophosphooxyether methacrylate (manufactured by Yushi Products Co., Ltd. 1)
A radiation-curable pressure-sensitive adhesive composition was prepared by adding 5 parts of Hosmer M). Next, as Example 1 of the VC comparison, the above-mentioned composition of lauryl mercaptan was selected, and as Comparative Example 2, the above-mentioned composition except for acid phosphooxyethyl methacrylate was selected.
A comparison of film properties was made.

BL film Q, part 7 is treated with IL composition and silicone 7
Apply C 1 to pattern 1/C-foot thickness (approximately 1111n),
Linear filament type kameko beam irradiation device (Energ)
yScience Inc, back, Ik product name, electrocurtain), force 11 speed m pressure 16[ ] kV, beam jtbtAu 10mA? 5 Mrad QJ'y children under a hydrating atmosphere (oxygen 1fcool4)
I k 11 (from 1 shot jin and vt,) J (h,),
It was created by reticulating it. Then, the elongation rate and rupture using a ketensilon tensile tester (81A) r!
+ degree ke 6111 returned 0 kasu shu is table 1 trace 9 and 1 ko O
a2, drawing length 9 speed is 20 on 1 m/min (rolls at 20°C).

The composition of Example 1 was found to have rubbery properties, and then the composition of Example 1 was heated to 0.025 mmP.
A layer of adhesive was applied to a polyester 2 film (manufactured by Toshikukiki Co., Ltd., trade name: Lumirror #25) of 0.015 mm Vcm, and irradiated with an electron beam in the same manner as described above. Laminated tag? f'' was manufactured, and the contact force and cohesive force were measured.The results are shown below.

Table 2 Comparison of Laminated Tea Grid % Note) υ Measured according to JIs-C-2107vL (Target body: SUS 450 BA board) 2) 65°C heating accelerated test for 7 days, contact force υ J strength l Shown as purple%.

(The smaller the increase, the better) 6) After 50 minutes at 20°C with both nails weighing 500g on a Bakelite board, the distance was 011j.

As a result, it is a viscous adhesive with a constant C/J # strength and little weathering over time, so it is clear that it is a pressure-sensitive adhesive with excellent properties.

Example 2, Comparison 13'16.4 50 parts of ethyl acrylate, 10 parts of 2''-ethylhexyl acrylate (4011.glycidyl methacrylate) were combined in the same manner as in Example 1, and 5 parts of acrylic acid was added. Acrylic yarn's radiation-touch-curing quasi-shaped oligomers are added to this oligomer, carbon tetrabromide, 10 esters, and phthalate (acryloyl ox-7 ether) to form a radiation-graded pressure-sensitive bonding agent composition. Kinsaku) I got it.υ
Cl/C ratio yield 5 comparison t is only carbon tetrabromide removed, ratio M
? For lJ4, we selected hydrogen phthalate, acrylo-j)''V oxyether, and a paraboloid. , the thickness of the adhesive layer is 0.00
5mm J: Apply 9Vt, Kameko Alffl J
ift 44.

All laminated films for surface protection were manufactured, and one intramuscular injection was performed.

Complete table of results 5 0 shown with Vt case stop 4) SOS bag JISB 7 with laminated 2 illumke pasted
7 7 71/cr16, 8rnmx Rikusen 9
It is clear from Table 6 that L5 vc has little weathering over time and has good drawing properties. Understood.

Claims (1)

[Claims] 1. Radical cross-linkable ethylenic vesicle Oon Radiation-curable liquid oligomer with double bond in the molecule
0.2 to 20 stopper parts of the chain transfer agent and 0.5 to 50 M parts of the monomer having an acidic group to n parts? A radiation-curable pressure-sensitive adhesive composition having all the following characteristics: