JP3165939B2 - UV curable paint and optical disc - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable paint suitable for use as a protective film of, for example, a compact disk or a magneto-optical disk , and an optical disk using the same .

[0002]

2. Description of the Related Art Optical disks such as compact disks and magneto-optical disks have a structure having a metal thin film layer formed by vapor deposition or sputtering on a transparent substrate such as polycarbonate. ing. This metal thin film layer is affected by oxygen and moisture in the air and its characteristics are apt to be deteriorated. Therefore, a UV-curable resin or the like has been conventionally used as a protective film. Generally, a spin coating method is employed as a coating method.

Further, when the thickness of the protective film of the recording layer of the optical disk is increased, the substrate tends to be warped. As a result, the device misreads or cannot read the recorded information. Need to be thinner. Therefore, the overcoat composition used in the spin coating method is required to have low viscosity.

However, particularly low molecular weight and low viscosity compounds used in photocurable resin compositions are generally used.
Primary skin irritation index (Primary Irritation Index)
Due to the high “PII value” , some problems have been reported in which the maintainer of the manufacturing apparatus touches the photocurable resin composition and is rash.

In addition to this problem, the UV curable resin currently used as a protective film for a compact disk is a UV ink for a label printed on the protective film because the cured film is yellow and transparent. There is also a problem that the color does not develop clearly. In particular, a light color such as white largely depends on the color of the protective film.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has an ultraviolet curable paint having low skin irritation and a colorless and transparent cured film , and an optical disc using the same.
The purpose is to obtain

[0007]

The ultraviolet-curable coating composition of the present invention comprises (meth) acrylic acid ester, a photopolymerization initiator and
In UV-curable coatings composed of photopolymerization accelerators,
T) acrylates have a PII value of 2 or less, and 3
A (meth) acryl having at least two (meth) acryloyl groups
30 to 60 parts by weight of the total amount of the lylic acid ester and 2 or less
Having a PII value and two (meth) acryloyl groups
(Meth) acrylic acid ester is 20 to 50 parts by weight in total
And a PII value of 2 or less and one (meth) acryloy
(Meth) acrylic acid ester having a hydroxyl group
And the photopolymerization initiator is a benzophenone-based photopolymerization initiator.
Initiator and acetophenone-based photopolymerization initiator
The promoter contains a tertiary amine-based polymerization accelerator and initiates photopolymerization.
Benzophenone-based photopolymerization
Initiator: tertiary amine photopolymerization accelerator: acetophenone
The polymerization initiator is 1: 2: 5-10.

[0008] The ultraviolet-curable coating material of the present invention, Ben
Zophenone-based polymerization initiator, tertiary amine photopolymerization accelerator and
And acetophenone-based polymerization initiator is (meth) acrylic acid
1 to 20 parts by weight per 100 parts by weight of ester
It is of the above-mentioned configuration contained.

[0009] Further, the ultraviolet-curable paint of the present invention further comprises
And an adhesion promoter (meth) acrylate 100
The above-mentioned amount added in the range of 0.1 to 5 parts by weight with respect to parts by weight
It is of a configuration.

Further, the ultraviolet-curable paint of the present invention can be used for bonding.
The promoter is ethylene oxide-modified succinic acid (meth) a
Acrylate, ethylene oxide modified phthalic acid (meth)
Acrylate, ethylene oxide modified phosphoric acid (meth)
It is the above-mentioned structure which is an acrylate. In addition,
For the optical disk of Ming, the UV-curable paint of the above configuration
Coated as a disk protective film and cured with UV light
It is a thing. Further, the ultraviolet-curable coating material of the present invention
Or more (meth) acrylates, photopolymerization initiators and
UV curable coatings composed of
The weight fraction of (meth) acrylic acid ester
The weight average value obtained by multiplying by the II value is 2 or less,
The initiator is a benzophenone-based photopolymerization initiator and acetophen
It is composed of a non-photopolymerization initiator.
A photopolymerization initiator comprising an amine polymerization accelerator and the photopolymerization
When the weight ratio of the accelerator is benzophenone-based photopolymerization initiator:
Tertiary amine photopolymerization accelerator: acetophenone polymerization initiator
= 1: 2: 5-10. In addition, the present invention
UV-curable paints have three or more (meth) acryloyl
(Meth) acrylic acid ester having a group
Oxide-modified trimethylolpropane triacrylate
And the above-described configuration. In addition, the ultraviolet hardening of the present invention
Coatings have three or more (meth) acryloyl groups
(Meth) acrylic acid ester is ethylene oxide
A modified trimethylolpropane triacrylate,
(Meth) acryl having two (meth) acryloyl groups
Lulic acid ester is neopentyl hydroxypivalate
It is the above-mentioned structure which is a recall diacrylate.
In addition, the ultraviolet-curable paint of the present invention has three or more
(T) Esters of (meth) acrylic acid having acryloyl groups
Is ethylene oxide-modified trimethylolpropane
Triacrylate, two (meth) acryloyl
(Meth) acrylates having a group are hydroxy
Neopentyl glycol diacrylate pivalate
(Meth) acrylate having one (meth) acryloyl group
Crylate esters are phenoxyethyl acrylate,
In or phenoxy Siji ethylene glycol acrylate
It has a certain configuration. Also, the ultraviolet curing of the present invention
Mold paint has three or more (meth) acryloyl groups
(Meth) acrylic acid ester is an ethylene oxide
Trimethylolpropane triacrylate, 2
(Meth) acryl having two (meth) acryloyl groups
Acid esters are neopentylglycol hydroxypivalate
Coal diacrylate, one (meth) acrylo
The (meth) acrylate having an yl group is pheno
Xyethyl acrylate or phenoxydiethylene
Glycol acrylate
The initiator is of the above configuration which is benzophenone.
You. In addition, the ultraviolet-curable paint of the present invention has three or more
(Meth) acrylic acid having a (meth) acryloyl group
Stele is ethylene oxide modified trimethylol pro
Pan triacrylate, two (meth) acrylo
(Meth) acrylates having an yl group are
Neopentyl glycol diacrylate xipivalate
Having one (meth) acryloyl group (meth)
T) Acrylic acid ester is phenoxyethyl acryle
Or phenoxydiethylene glycol acryle
Benzophenone-based photopolymerization initiator
Phenone, and the acetophenone-based photopolymerization initiator is 1
The above being a hydroxycyclohexyl phenyl ketone
It is of a configuration. Further, the ultraviolet-curable paint of the present invention
Has three or more (meth) acryloyl groups (
(T) Acrylic esters are ethylene oxide-modified
Limethylolpropane triacrylate, two
(Meth) acrylic acid having a (meth) acryloyl group
Stele is neopentyl glyco hydroxypivalate
Rudiacrylate, one (meth) acryloyl
(Meth) acrylates having a phenol group
Ethyl acrylate or phenoxydiethylene glycol
It is a coal acrylate and is a benzophenone-based photopolymerizable
The initiator is benzophenone, an acetophenone-based photopolymer.
The initiator is 1-hydroxycyclohexylphenyl ketone.
And the tertiary amine-based polymerization accelerator is 4-dimethyl
It is of the above configuration, which is ethyl ruaminobenzoate.

[0011]

According to the ultraviolet curable paint of the present invention, (meth)
Acrylic acid ester, photopolymerization initiator and photopolymerization accelerator
(Meth) acrylic acid
Esters have PII values of 2 or less and 3 or more (me
(T) Esters of (meth) acrylic acid having an acryloyl group
30 to 60 parts by weight, PII value of 2 or less, and
(Meth) acryl having two (meth) acryloyl groups
20 to 50 parts by weight of the total amount of the lylic acid ester and 2 or less
Having a PII value and one (meth) acryloyl group
Containing 5 to 25 parts by weight of (meth) acrylic acid ester,
The polymerization initiator is a benzophenone-based photopolymerization initiator and
A phenone-based photopolymerization initiator;
Contains a secondary amine-based polymerization accelerator, and promotes photopolymerization with a photopolymerization initiator.
Weight ratio of the benzophenone-based photopolymerization initiator:
Amine photopolymerization accelerator: acetophenone polymerization initiator =
Since it is 1: 2: 5 to 10, it is possible to obtain a coating agent having low skin irritation and low viscosity, and the cured film can be changed from yellow transparent to colorless transparent.

[0012]

EXAMPLES Examples of the UV-curable coating material of the present invention will be described below.

The abbreviations of the compositions used in the examples and comparative examples are as follows. Trifunctional (meth) acrylic ester (three (meth) acrylic
(Meth) acrylic acid ester having a liloyl group) 3EO-TMPTA: Ethylene oxide-modified trimethylolpropane triacrylate ( PII value = 1.0 , Shin-Nakamura Chemical) bifunctional (meth) acrylic ester (two (meth) acryloyl) having a group (meth) acrylic acid ester) MANDA: hydroxypivalic acid neopentyl glycol diacrylate rate (PII value = 1.25, Japan Kayaku) Futtoma 4160: propylene oxide-modified neopentyl glycol diacrylate (PII value = 2. 3, Nopco) having one (meth) acryloyl group-containing (meth) acrylic acid ester Po-a: phenoxyethyl acrylate (PII value = 1.5, Kyoeisha Yushi) M-101: phenoxy diethyleneglycol acrylate PII value = 0.7, Toa Gosei) having an adhesion promoter (two (meth) acryloyl group-containing (meth) acrylic acid ester le) PM-2: ethylene oxide-modified phosphoric acid dimethacrylate (PII value = 3.3 , Nippon Kayaku) polymerization initiator 184: 1-hydroxycyclohexyl phenyl ketone 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck) BP100: benzophenone polymerization accelerator EPA: 4-dimethylaminobenzoic Ethyl acid

The composition ratios of the compositions of Examples 1 to 6 and Comparative Examples 1 and 2 are as shown in Table 1.

[0015]

[Table 1]

Example 1 30 parts by weight of 3EO-TMPTA as a polyfunctional acrylate, 50 parts by weight of MANDA, and Po-A as a diluent
20 parts by weight, 0.1 part by weight of PM-2 as an adhesion promoter, 5 parts by weight of 184 as an initiator, and 1 part by weight of BP100.
Using 2 parts by weight of EPA and 2 parts by weight of EPA, they were uniformly mixed to obtain a coating agent.

Example 2 In Example 1, 3EO- was used as the polyfunctional acrylate.
A coating agent was prepared in the same manner as in Example 1 except that TMPTA was changed to 40 parts by weight and MANDA was changed to 40 parts by weight.

Example 3 50 parts by weight of 3EO-TMPTA as a polyfunctional acrylate, 30 parts by weight of MANDA, and Po-A as a diluent
20 parts by weight, 0.1 part by weight of PM-2 as an adhesion promoter, 7 parts by weight of 184 as an initiator, and 1 part by weight of BP100.
Using 2 parts by weight of EPA and 2 parts by weight of EPA, they were uniformly mixed to obtain a coating agent.

Example 4 In Example 3, the polyfunctional acrylate was 3EO-
A coating agent was prepared in the same manner as in Example 3 except that TMPTA was changed to 60 parts by weight and MANDA was changed to 20 parts by weight.

Example 5 60 parts by weight of 3EO-TMPTA as a polyfunctional acrylate, 30 parts by weight of MANDA, and Po-A as a diluent
, 10 parts by weight of PM-2 as an adhesion promoter, 10 parts by weight of 184 as an initiator, 1 part by weight of BP100, and 2 parts by weight of EPA, and uniformly mixed. A coating agent was used.

Example 6 In Example 5, 3EO- was used as the polyfunctional acrylate.
TMPTA was changed to 40 parts by weight, MANDA was changed to 40 parts by weight, and PO-A (10 parts by weight) used as a diluent was changed to M.
Except having changed to -101 (20 weight part), it carried out similarly to Example 5, and set it as the coating agent.

Comparative Example 1 40 parts by weight of 3EO-TMPTA as a polyfunctional acrylate, 40 parts by weight of Photomer 4160 , 20 parts by weight of Po-A as a diluent, and 0.1 part by weight of PM-2 as an adhesion promoter Using 1173 parts by weight of 1173 as an initiator, the mixture was uniformly mixed to obtain a coating agent.

Comparative Example 2 In Comparative Example 1, 3EO-
A coating agent was prepared in the same manner as in Comparative Example 1 except that TMPTA was changed to 50 parts by weight, Photomer 4160 was changed to 45 parts by weight, and Po-A was changed to 5 parts by weight as a diluent.

The physical properties of the compositions of the above Examples and Comparative Examples were evaluated as follows. Table 1 also shows the results.

UV irradiation conditions UV irradiation device: UVC-2533 (Ushio Inc.) Metal halide lamp 1 input 120 W / cm Lamp height 10 cm Light intensity: 200 mJ / cm ² Light meter: UIT-102 (Ushio Inc.), light receiving: UVD
-365PD

Measurement of Viscosity The viscosity at 25 ° C. was measured using a cone-plate viscometer. The viscometer was from Haake, the sensor system was PK100, and the measurement system was Rofovisco RV20-M.
5. The sensor used PK5,1 °. On the other hand, the volume of the sample was 0.5 cm ³ , and the shear rate was 1000 s ^-1 / m.

Skin irritation A weight average value was estimated from the PII value of the raw material and the weight fraction of the composition, and the irritation was evaluated based on the values as shown in Table 2. The numerical values are classified into the range of 0 to 8, and the smaller the value, the lower the irritation.

[0028]

[Table 2]

Each sample was applied on a glass plate using a coil bar # 12 and irradiated with ultraviolet rays under the above conditions to obtain a cured film. The hardness of the surface of the pencil was measured based on JIS K5400 using Mitsubishi Uni.

Adhesion

First, the ultraviolet-curable resin compositions of Examples and Comparative Examples were spin-coated on a polycarbonate substrate having a diameter of 12 cm and a thickness of 1.2 mm on which aluminum was deposited,
The protective film having a thickness of about 7 μm was formed by irradiating ultraviolet rays under the above-described conditions and curing. In this case, as a spin coater, MIKASA SPINCOAT manufactured by Mikasa Corporation is used.
Use ER1 H-DXII and set the rotation speed to 3000RP.
M and the shaking-off time were changed depending on the viscosity, and the film thickness was uniformly adjusted. Make a cut in the cured film with the cutter knife to reach the aluminum deposition film with the cutter knife, apply cellophane tape along the cut, hold one end of the tape at right angles to the coating surface, and pull it instantaneously. Peel off.
As a result, when the cured film is peeled with the aluminum vapor-deposited film attached thereto, the adhesive force is set to “A”, and peeling occurs between the cured film and the aluminum vapor-deposited film, and the aluminum vapor-deposited film is about half on the polycarbonate substrate. The adhesive force when remaining was "B", and the adhesive force when all the aluminum vapor-deposited film remained on the polycarbonate substrate was "C".

Adhesion to Polycarbonate Plate A sample obtained by spin-coating a polycarbonate substrate as described above was cut into 100 cross-cuts on a cured film by a cutter knife so as to reach the polycarbonate substrate.
A cellophane tape is applied from above and one end of the tape is kept at right angles to the coating surface, and then instantaneously peeled off. The number of grids of the cured film remaining on the polycarbonate substrate was defined as the adhesion of the sample to the polycarbonate plate.

Corrosion resistance Aluminum deposited 12 cm in diameter, 1.2 m thick
A sample obtained by spin-coating a polycarbonate substrate of m length as described above was placed in an oven at 60 ° C. and 95% RH and aged for 100 hours, and the increase in pinholes due to corrosion of the Al layer was measured. This pinhole is as follows. That is, for example, metal Al is used for the reflection film of a compact disk, and for a magneto-optical disk, a dielectric film / magneto-optical recording film / dielectric film / reflection film (Al layer) is sequentially formed on the substrate by sputtering. These sputtered films are affected by oxygen and moisture in the air and are very susceptible to corrosion, so that they are coated with a protective film made of an organic material. The inorganic layer made of an inorganic material such as an Al layer is sandwiched between the base material and the protective film. Usually, in such a configuration, when illuminated by the light source from the lower surface of the disk and observed from the upper surface of the disk, the light cannot be confirmed because the light is blocked by the opaque inorganic layer. However, when the disk left under high temperature and high humidity is observed in the same manner, the light blocked by the opaque inorganic layer can be confirmed from the circular hole portion which is made transparent by corrosion. This hole is called a pinhole. In this embodiment, the size of the pinhole is set to 0 to 10 μm: 10 to 30 μm.
μm: 30-50 μm: 50-100 μm: 100 μm
Classified as above, pinholes of 100 μm or more and 50-
When a pinhole having a growth potential of 100 μm was confirmed, it was counted as having a pinhole, and the corrosivity was evaluated by the number as shown in Table 3.

[0034]

[Table 3]

First, the ultraviolet-curable resin compositions of Examples and Comparative Examples were spin-coated on a polycarbonate substrate having a diameter of 12 cm and a thickness of 1.2 mm on which aluminum was deposited, and cured by irradiating ultraviolet rays under the above conditions. A protective film having a thickness of about 7 μm was formed and evaluated visually. As shown in Table 4, the appearance was evaluated by the color of the cured film.

[0036]

[Table 4]

The results of the evaluation of the above-mentioned items for Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1.
As shown in FIG.

Looking at the evaluation results of Examples 1 to 6,
The viscosity is 23 to 33 mPa · s / 25 ° C., the PII value is A,
The hardness was H or 2H, the adhesion (vs. Al) was A, the adhesion (vs. Pc) was 100/100, the corrosion resistance was A, and the appearance was ○.

On the other hand, the evaluation results of Comparative Examples 1 and 2 show that the viscosity is 25 to 38 mPa · s / 25 ° C.
The II value was A, the hardness was H, the adhesion (vs. Al) was A, the adhesion (vs. Pc) was 100/100, and the corrosion resistance was A, which was satisfactory for the above items.
And it was not satisfactory.

The reason why the appearance was improved to be colorless and transparent in the example, while the appearance was yellow and transparent in the comparative example, was that the polymerization initiator was 1173 in the comparative example.
(2-Hydroxy-2-methyl-1-phenylpropan-1-one) was used, whereas 184 was used in the examples.
(1-hydroxycyclohexyl phenyl ketone), B
This is probably because P100 (benzophenone) and EPA (ethyl 4-dimethylaminobenzoate) were used.

The ethylene oxide-modified trifunctional (meth) acrylic ester used in the present invention includes, for example, trimethylolpropane triacrylate (NK ester A-TMPA-3Eo, Shin-Nakamura Chemical). If the use range is more than 70 parts by weight, the coating film formed from the coating agent is not preferred because the curing shrinkage and strain are increased, the adhesion to the substrate is poor, and the weather resistance is lowered. When the amount is 20 parts by weight or less, the coating film formed from the coating agent is easily scratched and the hardness of the film surface is low. Therefore, the range of use of this ethylene oxide-modified trifunctional (meth) acrylate is 20 to 70% by weight, preferably 30 to 60% by weight.

The bifunctional (meth) used in the present invention
As the acrylate, for example, hydroxypival
Neopentyl glycol diacrylate (MAND)
A) and the like. This use range is 5 to 75 parts by weight, preferably 20 to 50 parts by weight.

The phenoxyethyl acrylate or phenoxydiethylene glycol acrylate used in the present invention is a component having a diluting ability (low viscosity) and low skin irritation. When the use range exceeds 25 parts by weight, it is formed from the coating agent. The hardened coating film hardly hardens the film surface and also impairs the hardness. Further, when the use range is less than 5 parts by weight, the dilution effect tends to decrease, which is not preferable. Therefore, the usage range of the diluent monomer is preferably 5 to 25 parts by weight.

Of the photopolymerization initiators used in the present invention,
Examples of the acetophenone-based polymerization initiator include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, and 2-hydroxy-2-methyl-1-phenylpropane. -1-on,
1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-
On, 4- (2-hydroxyethoxy) -phenyl (2
-Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4
Examples of benzophenone-based polymerization initiators such as-(methylthio) phenyl) -2-morpholinopropane-1 include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, and 4-benzzoyl-4 '. -Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone and the like can be used. Particularly preferably, as the acetophenone-based polymerization initiator, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-
1- (4- (methylthio) phenyl) -2-morpholinopropane-1 is mentioned. Examples of the benzophenone-based polymerization initiator include benzophenone, benzoylbenzoic acid, and methyl benzoylbenzoate. Examples of the tertiary amine-based photopolymerization accelerator include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone,
4,4'-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butyne)
Ethyl, isoamyl 4-dimethylaminobenzoate, 4-
2-ethylhexyl dimethylaminobenzoate and the like can be used. Particularly preferably, the tertiary amine-based photopolymerization accelerator is ethyl 4-dimethylaminobenzoate,
Ethyl dimethylaminobenzoate (n-butyne) 4-
Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate and the like. As described above, the components of the photopolymerization initiator are used by combining three components of an acetophenone-based polymerization initiator, a benzophenone-based polymerization initiator, and a tertiary amine-based photopolymerization accelerator. The amount of each component is preferably 1 to 20% by weight of the overcoat composition for an optical disk, and particularly preferably 1 to 10% by weight for each component.

The ultraviolet-curable coating agent for an optical disk of the present invention can sufficiently achieve its intended purpose only with the above-mentioned component substances, but is conventionally known as far as the original characteristics are not changed in order to further improve the performance. The following components, for example, additives such as a leveling agent, an ultraviolet absorber, an antioxidant, a silane coupling agent, silicone oil, and an adhesion promoter may be appropriately included.

In particular, with respect to the corrosiveness, in order to further improve the adhesion having a deep relationship, an adhesion promoter such as ethylene oxide-modified succinic acid (methanoacrylate, ethylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified Adhesion can be improved by adding (meth) acrylate having a carboxyl group, a phosphoric acid group or a hydroxyl group, in addition to phosphoric acid (meth) acrylate, and these adhesion promoters can be used in the present invention. 0.1 to 100 parts by weight of the composition
5 parts by weight.

The ultraviolet curable coating agent of the present invention comprises
It is manufactured by blending the above-described components by a general blending method. In order to form a protective coating layer on an optical disk as a base material from the coating agent of the present invention, the compounded coating agent is filtered through a 0.2 μm membrane filter, and then a spin coater is used in a clean room to form a coating film of 5 to 10 μm. It may be applied in such a manner as described above, and then cured by irradiation with ultraviolet rays.

As the ultraviolet light source used in the present invention, a high-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, or the like can be used. In these methods, the curing of the optical disk material can be performed by electron beam irradiation instead of ultraviolet irradiation.

As described above, the coating agent of the present invention
It has low skin irritation, low viscosity, quick curing by ultraviolet rays, and a cured coating film having excellent surface hardness, adhesion and corrosion resistance is formed as a protective film for the optical disc substrate.

From the above, according to this example, 75 to 95 parts by weight of (meth) acrylic acid ester blended with EO-modified trifunctional and difunctional, phenoxyethyl acrylate or phenoxydiethylene glycol acrylate 5
To 25 parts by weight and a total of 100 parts by weight thereof, an acetophenone-based polymerization initiator, a benzophenone-based polymerization initiator, and an amine-based polymerization catalyst in combination to form a photopolymerization initiator 1
Since it contains 20 parts by weight, it is possible to obtain a coating agent having low skin irritation and low viscosity, which eliminates the "rash" of the maintainer of the manufacturing apparatus, and has good applicability and good workability in manufacturing. Is effective. In addition, it is quickly cured by ultraviolet rays, has excellent adhesion and hardness, and is an extremely good protective film against corrosion of a metal thin film layer in an environmental resistance test, thereby improving the reliability of products. In addition, the cured film can be changed from yellow transparent to colorless and transparent, and the coloring of the printing ink can be made clearer.

It should be noted that the present invention is not limited to the above-described embodiment, but can adopt various other configurations without departing from the gist of the present invention.

[0052]

As described above, according to the present invention,
It is possible to obtain a coating agent with low skin irritation and low viscosity, which has the effect of eliminating "rash" of the maintainer of the manufacturing apparatus, and having good applicability and good workability in manufacturing. In addition, it is rapidly cured by ultraviolet rays, has excellent adhesion and hardness, and has an extremely good protection film against corrosion of a metal thin film layer in an environmental resistance test, thereby improving product reliability. In addition, the cured film can be changed from yellow transparent to colorless and transparent, and the coloring of the printing ink can be made clearer.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-90516 (JP, A) JP-A-4-146971 (JP, A) JP-A-7-70472 (JP, A) JP-A-3- 172358 (JP, A) JP-A-2-6562 (JP, A) JP-A-4-149280 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 4/02 C09D 5 / 00

Claims (12)

(57) [Claims] (1) a (meth) acrylic acid ester, a photopolymerized
UV curable paint consisting of initiator and photopolymerization accelerator
The (meth) acrylic acid ester has a primary skin irritation rate value of 2 or less (hereinafter referred to as “PII value”).
U), and having three or more (meth) acryloyl groups
(Meth) acrylic acid ester is 30 to 60 parts by weight in total
And a PII value of 2 or less and two (meth) acryloyl groups
(Meth) acrylate having 20 to 5 in total
0 parts by weight, a PII value of 2 or less, and one (meth) acryloyl group
(Meth) acrylic acid ester having 5 to 25 parts by weight
Wherein, the photopolymerization initiator include benzophenone-based photopolymerization initiator and acetone
A photopolymerization initiator containing a tertiary amine-based polymerization initiator, wherein the weight ratio of the photopolymerization initiator to the photopolymerization accelerator is benzopheno.
Photopolymerization initiator: tertiary amine photopolymerization accelerator: aceto
Phenone-based polymerization initiator = 1: 2: that it is 5 to 10
Characteristic UV curable paint. 2. A benzophenone-based polymerization initiator,
Min photopolymerization accelerator and acetophenone-based polymerization initiator,
1 to 100 parts by weight of (meth) acrylate
2. The ultraviolet according to claim 1, which is contained in an amount of 20 parts by weight.
Line-curable paint. 3. The method of claim 1 , wherein the adhesion promoter is (meth) acrylic.
0.1 to 5 parts by weight based on 100 parts by weight of the acid ester
The ultraviolet hardener according to claim 1 or 2, which is added by:
Chemical paint. 4. The adhesion promoter is modified with ethylene oxide.
Succinic (meth) acrylate, ethylene oxide modified
Phthalic acid (meth) acrylate or ethylene oxide
4. A side-modified phosphoric acid (meth) acrylate.
The ultraviolet-curable paint according to the above. 5. The ultraviolet curing according to claim 1
Mold paint as a protective film for the optical disk
An optical disk that has been cured externally. 6. Two or more (meth) acrylate esters
UV curing consisting of photopolymerization initiator and photopolymerization accelerator
In the mold paint, the weight fraction of each (meth) acrylate
The weight average value obtained by multiplying the PII value is 2 or less, and the photopolymerization initiator is a benzophenone-based photopolymerization initiator and
The photopolymerization accelerator comprises a tertiary amine-based polymerization accelerator.
Ri, the weight ratio of the photopolymerization initiator and photopolymerization accelerator is Benzofu
Enone photopolymerization initiator: tertiary amine photopolymerization accelerator: a
Acetophenone-based polymerization initiator = 1: 2: This is a 5-10
And a UV-curable paint. 7. It has three or more (meth) acryloyl groups.
(Meth) acrylic acid ester is ethylene oxide
Modified trimethylolpropane triacrylate
The ultraviolet-curable paint according to claim 1. 8. It has three or more (meth) acryloyl groups.
(Meth) acrylic acid ester is ethylene oxide
Modified trimethylolpropane triacrylate
Ri has two (meth) acryloyl group-containing (meth) acrylate
Lulic acid ester is neopentyl hydroxypivalate
The ultraviolet ray hardener according to claim 1, which is recall diacrylate.
Chemical paint. 9. It has three or more (meth) acryloyl groups.
(Meth) acrylic acid ester is ethylene oxide
Modified trimethylolpropane triacrylate
Ri has two (meth) acryloyl group-containing (meth) acrylate
Lulic acid ester is neopentyl hydroxypivalate
A recall diacrylate, having one (meth) acryloyl group-containing (meth) acrylate
Lulic esters are phenoxyethyl acrylate and
Is phenoxydiethylene glycol acrylate
The ultraviolet-curable paint according to claim 1. 10. The method according to claim 1, wherein three or more (meth) acryloyl groups are
(Meth) acrylic acid ester having ethylene oxalate
Iid-modified trimethylolpropane triacrylate
Ri has two (meth) acryloyl group-containing (meth) acrylate
Lulic acid ester is neopentyl hydroxypivalate
A recall diacrylate, having one (meth) acryloyl group-containing (meth) acrylate
Lulic esters are phenoxyethyl acrylate and
Is phenoxydiethylene glycol acrylate
The benzophenone-based photopolymerization initiator is benzophenone.
The ultraviolet-curable paint according to claim 1. 11. The method according to claim 11, wherein three or more (meth) acryloyl groups are
(Meth) acrylic acid ester having ethylene oxalate
Iid-modified trimethylolpropane triacrylate
Ri has two (meth) acryloyl group-containing (meth) acrylate
Lulic acid ester is neopentyl hydroxypivalate
A recall diacrylate, having one (meth) acryloyl group-containing (meth) acrylate
Lulic esters are phenoxyethyl acrylate and
Is phenoxydiethylene glycol acrylate
The benzophenone-based photopolymerization initiator is benzophenone.
Ri, acetophenone photopolymerization initiator, 1-hydroxy-sik
2. The ultraviolet light according to claim 1, which is rohexyl phenyl ketone.
Curable paint. 12. The method according to claim 12, wherein three or more (meth) acryloyl groups are
(Meth) acrylic acid ester having ethylene oxalate
Iid-modified trimethylolpropane triacrylate
Ri has two (meth) acryloyl group-containing (meth) acrylate
Lulic acid ester is neopentyl hydroxypivalate
A recall diacrylate, having one (meth) acryloyl group-containing (meth) acrylate
Lulic esters are phenoxyethyl acrylate and
Is phenoxydiethylene glycol acrylate
The benzophenone-based photopolymerization initiator is benzophenone.
Ri, acetophenone photopolymerization initiator, 1-hydroxy-sik
Rohexyl phenyl ketone, and the tertiary amine-based polymerization accelerator is 4-dimethylaminobenzoate
The UV-curable coating according to claim 1, which is ethyl fragrance.