JPH01308415A - Actinic radiation-curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent adhesion to acrylic resin and being useful for disc information recording media, by mixing a specified polymerizable compound with a specified polymerization initiator. CONSTITUTION:100pts.wt. at least one polymerizable compound selected from a compound of formula I [wherein R is H or a (meth)acryloyl group, a1, a2, b1, b2, c1, c2, d1 and d2 are each 0 or >=1, a1+a2not equal to 0, b1+b2not equal to 0, c1+c2not equal to 0, and d1+d2not equal to 0] and a compound of formula II [wherein e1, e2, f1, f2, g1, g2, h1, h2, i1, i2, j1 and j2 are each a1, e1+e2not equal to 0, f1+f2not equal to 0, g1+g2not equal to 0, h1+h2not equal to 0 and i1+i2not equal to 0) is mixed with, desirably, 1-10pts.wt. at least one polymerization initiator comprising a compound of formula III or IV (wherein R is CH(CH3) or CH2.CH (CH3)2].

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an active energy ray-curable resin composition suitable for methods of duplicating disk-shaped recording carriers.

<Prior art> In recent years, disc-shaped information recording carrier duplication molds (stambar) have been developed.
Using high quality? As a method for manufacturing Jll disks, a method using a liquid resin that is cured by irradiation with ultraviolet rays or the like is attracting attention.

This method involves filling the gap between the stand bar and the optically transparent base material with a photocurable liquid resin, and irradiating the transparent resin base material with ultraviolet rays to harden the liquid resin, thereby integrating the resin into the transparent base material. This is a method in which the film is oxidized and then peeled off from the stand bar. In the replicated disk having a resin layer with an uneven surface manufactured by this method, a thin metal layer whose optical state changes by laser beam irradiation is then formed on the surface of the resin layer by vacuum evaporation. The properties required for the photocurable liquid resin produced by this method are transparency and low viscosity, good photocurability, good releasability from the stand bar, and the ability to be used as a transparent base material. Examples include good adhesion with a suitable acrylic resin and no residual volatile substances.

As photocurable resins, resin compositions containing adducts of acrylic acid and epoxy resins, bifunctional esters of acrylic acid, and monofunctional esters of acrylic acid (Japanese Patent Application Laid-open No.
No. 7-88503) has been proposed, but although this composition has good releasability from the stand bar, it has insufficient adhesion to the acrylic resin of the transparent base material, resulting in signal deterioration and signal deterioration. This may cause problems such as defects.

In addition, the applicant previously developed a method of combining hydroxypropyl acrylate and a diisocyanate compound as a curable liquid resin.
A resin composition (Japanese Unexamined Patent Publication No. 60-2061315) was proposed that contains urethane acrylate, which is an addition reaction product, as a main component. However, although this composition has good releasability with the nickel stamper and good initial adhesion with the acrylic resin that is the transparent base material, the composition does not adhere after being held at 50°C and relative humidity of 98°C or more for 24 hours. It was found that the so-called secondary adhesion was insufficient, and long-term use was problematic.

As a method of obtaining adhesion that can withstand long-term use, a method of polishing the surface of the base material (Japanese Patent Application Laid-open No. 62-277475) has been proposed, but an increase in cost due to the addition of steps cannot be avoided. Under these circumstances, there is a strong demand for the development of an active energy ray-curable liquid resin that adheres well to an acrylic resin substrate not only initially but also for a long period of time without any treatment of the acrylic resin substrate.

Problems to be Solved by the Present Invention The purpose of the present invention is to provide an active energy V-ray curable composition that has good adhesion to an acrylic resin substrate not only initially but also over a long period of time. It is about providing.

Means for Solving Problems> The present invention comprises (A) at least one polymerizable compound selected from general formulas (I) and (II), and (B) at least one polymerizable compound represented by the following structural formula. It is an active double V-ray curable composition comprising an initiator.

R(OHtO pigeon(04)alO(OHx)(H,(OH
tO). , R (I) (C horse) dl- (O horse 0) d,
R However, R is a hydrogen atom or a (meth)acryloyl group, and not all of them are hydrogen atoms.

Also, 'Is' 1m bl-b goose m J* 02m d
lm '4 is an integer of 0 or 1 or more, and is a, + a, 〆O b, 〆O, 〆O Ql +c2〆0 (I1 + dj〆0).

R(OHz C) g, (Hz C) g, (
CH*), 11(CFi鵞0)j, RHowever, R is a hydrogen atom or a (meth)acryloyl group, and not all are hydrogen atoms. Also, el m e meaning e fl
e hogl a gas hl * hls 1i
eiz* jt, h is an integer greater than or equal to 0, e, +θ, meO f, +f, meO g+tengz〆O hm-)-h=〆O 11+i, 〆O j1+, h, I 'O.

Polymerization initiator (B) 0-R(7) Polymerizable compound (A) represented by general formula (I) or (n)
,! Examples of - include neobentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, and the like. Among them, neopentyl glycol diacrylate shows particularly excellent performance.

Examples of the polymerization initiator (B) include benzophenone, benzyl, benzoin butyl ether, benzoin propyl ether, and 5-dimethyl-4-methoxybenzophenone. Among these, benzophenone is particularly preferred.

In the present invention, it is desirable to blend the polymerization initiator (B) in an amount of 1 to 10 parts by weight with respect to 100 M parts of the polymerizable compound (A). If the polymerization initiator (B) is less than 1 part by weight, the activation to light tends to be insufficient, and if it exceeds 10 parts by weight, the adhesion strength tends to decrease, and it is also preferable from the viewpoint of cost. ,<do not have.

In the present invention, in addition to the polymerizable compound (A), various active energy ray-curable compounds, various polymers, plastic compositions, or various additives may be blended within the range that does not impair the effects of the present invention.

As the light source used for curing the composition of the present invention, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, an arc lamp, a gallium lamp, etc. are used.

Next, the present invention will be explained using examples. In the examples, parts indicate parts by weight.

<Examples 1 to 4 and Comparative Examples 1 to 3> (Production of urethane diacrylate 1) 80 parts of quinone diisocyanate and 12 parts of hydroquinone methyl ether were added to a flask, and while stirring at 70°C, 2-hydroxypropyl ether was added. A mixture of 116 parts of /L/1 and 04 parts of dibu-1,000 tin dilaurate was added dropwise over 3 hours.

After the dropwise addition was completed, the reaction was further carried out at 70°C for 3 hours to obtain urethane diacrylate 1 47'c.

(Production of urethane diacrylate 2) Instead of 2-hydroxypropyl methacrylate,
Urethane diacrylate 2 was obtained in the same manner as in the production of urethane diacrylate 1, except that 110 parts of 2-hydroxyethyl acrylate was used.

(Manufacture of epoxy acrylate 1) Ebiko in a flask) 828 (manufactured by Yuka Shell ■) 100
1 part, 40 parts of acrylic acid, and 1.5 parts of dimethylaminoethyl methacrylate were added, and while stirring, heated at 70°C for 1 hour, then at 80°C for 1 hour, then at 90°C for 1 hour, and then heated at 90°C for 1 hour. Heating was continued until the acid value decreased to 5 or less at °C to obtain epoxy acrylate 1.

Active energy ray curable composition A with the compounding ratio shown in Table 1
- Adjusted G. The compositions A to G were uniformly coated onto a stambar manufactured by AVM Co., Ltd. using a bar coater ÷40.

Next, spacers with a thickness of about 50 μm were placed on the four corners of the stand bar, and an acrylic resin plate with a thickness of about 1.5 m without the addition of ultraviolet absorbers (Acrylite II-oo manufactured by Mitsubishi Rayon ■) was placed on each corner of the stand bar.
o) were stacked one on top of the other so as not to introduce air bubbles. Then, ultraviolet rays were irradiated from the acrylic resin plate side. The irradiation energy at this time is the light intensity at 350 nm, and is 1
It was 200 mj/c-.

The evaluation results regarding the adhesion between the acrylic resin plate obtained as described above and the cured product are as shown in Table 1.

In addition, the adhesion was evaluated by a goblin Cellotape peeling test using J-Ko8 K-5400, and was expressed as an adhesion rate.

Table 1 (Assembly part) *1) Adhesion after moisture resistance was measured after being left in an atmosphere of 98% RH and 50°C for 300 hours.

<Effects of the Invention> As detailed above, the active energy ray-curable composition of the present invention has excellent initial and long-term adhesion to the acrylic resin after curing, so that it can be used to create disc-shaped information. It can be used as an adhesive with acrylic resins for recording carriers and various other uses, and can exhibit excellent effects.

Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney Toshio Yoshizawa

Claims (1)

[Claims] Consisting of (A) at least one polymerizable compound selected from general formulas (I) and (II), and (B) at least one polymerization initiator represented by the following structural formula: Active energy ray curable composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, R is a hydrogen atom or a (meth)acryloyl group, and not all of them are hydrogen atoms. Also, a_1, a_2, b_1, b_2, c_1, c_2
, d_1, and d_2 are 0 or an integer greater than or equal to 1, and a_1+a_2≠0 b_1+b_2≠0 c_1+c_2≠0 d_1+d_2≠0. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) However, R is a hydrogen atom or a (meth)acryloyl group, and not all of them are hydrogen atoms. Also, e_1, e_2, f_1, f_2, g_1, g_2
, h_1, h_2, i_1, i_2, j_1, and j_2 are 0 or an integer greater than or equal to 1, and e_1+e_2≠0 f_1+f_2≠0 g_1+g_2≠0 h_1+h_2≠0 i_1+i_2≠0 j_1+j_2≠0. <Polymerization initiator (B)> ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R; CH(CH_3)_2 or CH_2CH(CH_3)_2) ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼