JPS59232155A - Ultraviolet-curing marking ink - Google Patents

Abstract

PURPOSE:To provide a marking ink which can be easily cured by ultraviolet light irradiation and has excellent adhesion and solvent resistance, by mixing a specified cation-polymerizable compd., a photopolymerization initiator capable of releasing a Lewis acid catalyst by ultraviolet light irradiation and a pigment. CONSTITUTION:At least one cation-polymerizable compd. (A) mainly composed of an epoxy resin contg. at least two oxirane rings per molecule (e.g. bisphenol A type epoxy resin), 0.5-10wt% (based on the weight of component A) photopolymerization initiator (B) (e.g. 4,4'-dimethyldiphenyliodonium hexafluorophosphate) capable of releasing a Lewis acid catalyst (capable of initiating the polymn. of component A) by ultraviolet light irradiation, and 5-30wt% (based on the weight of component A) leafing type scaly aluminun powder as a pigment and 1-30wt% (based on the weight of component A) silica powder (C) are mixed together to obtain the desired ultraviolet-curing marking ink.

Description

[Detailed description of the invention] The present invention is easily cured by ultraviolet irradiation, and P'! ″′.

The present invention relates to an ultraviolet curable marking ink having excellent adhesion and solvent resistance.

Conventionally known ultraviolet curable marking inks use acrylate resins such as epoxy acrylate, epoxy methacrylate, acrylic ester, methacrylic ester, and unsaturated polyester, and acids, and are less effective than thermosetting marking inks. The characteristics required for marking ink used for marking 0 and 0 chips, which have significantly poor adhesion, are as follows:
The adhesion is poor because the chips go through processes such as solder dipping and solvent cleaning, and pass through an automatic insertion machine.
It has excellent solvent resistance and abrasion resistance.

However, the conventional ultraviolet curable marking ink lacks high reliability with respect to the above-mentioned characteristics, so it is currently not used for marking the C-chip.

In view of the above-mentioned circumstances, the present inventors have realized that
As a result of intensive research aimed at developing a UV-curable marking ink with excellent adhesion to substrates and solvent resistance, we found that (A) the main component is an epoxy resin with two or more oxirane rings in one molecule. (B) one or more cationically polymerizable compounds (hereinafter referred to as component A); 0.5-10 for the compound
% (weight %, the same shall apply hereinafter) of a photoinitiator (hereinafter referred to as component B) and (0) a glue type scale-like aluminum powder in an amount of 5 to 30% based on the resin component as a pigment and 1 to 3
The present invention was completed based on the discovery that an ultraviolet curable marking ink characterized by comprising 0% silica powder (hereinafter referred to as O component) has excellent adhesion to substrates and solvent resistance. In other words, the present inventors created an ultraviolet curable resin composition by adding a photoinitiator that can liberate a Lewis acid catalyst upon irradiation with ultraviolet rays to an epoxy resin that has excellent adhesion and mechanical properties. After that, when we used the composition as a UV-curable marking ink containing a single-finging type aluminum powder as a pigment and a silica powder with excellent UV transparency, we found that it had excellent adhesion and resistance. It has been discovered that it provides solvent properties, surface hardness, and metallic luster.

The cationic polymerizable compound of component A used in the present invention is 1
The main component is an epoxy resin having two or more oxirane rings in the molecule, and preferred examples include bisphenol A epoxy resin, novolac epoxy resin, and alicyclic epoxy resin.

Such bisphenol A type epoxy resins include Epicote 828, Epicote 834, Epicote 834, Epicote 1001, Epicote 10.
04, 1007 (all manufactured by Shell Chemical Co., Ltd., product names)
, DKR331, DKR332, DKR661, DKR664, DKR6
67 (manufactured by Dow Chemical Company, product name), Araldite 260, Araldite 280, Araldite 6071, Araldite 6084, Araldite 60
97 (trade name, manufactured by Ciba Geigy), etc., and these may be used alone or in combination.

In addition, the novolak type epoxy resin is Ebiko)
152, 154 (all manufactured by Shell Chemical Co., Ltd., trade names),
Araldite ηPN113B, 11! PN11+9,
Same 11tON 1235, Same 11t□N1275, Same 1
1:0N1280, FtON1299 (trade name, manufactured by Ciba Geigy), D1nN431, 438 (
(1 trade name manufactured by Dow Chemical Company) and the like, and these may be used alone or in combination.

Furthermore, as the alicyclic epoxy resin, Araldite 0
Y175, 0Y177, 0YI79, 0Y184
, 0Y192 (all manufactured by Ciba Geigy, product name)
etc.

Other butadiene-based epoxy resins can also be used, and mixtures of the various epoxy resins mentioned above can also be used.

Furthermore, monofunctional epoxy diluents and acid anhydride curing agents may also be used within the range of not deteriorating the curing properties.

Examples of such monofunctional epoxy diluents include phenyl glycidyl ether and t-butyl glycidyl ether, and examples of acid anhydride curing agents include Anhydrous Bita Meritz).
acid, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc.

Furthermore, it is also possible to use a cationically polymerizable vinyl compound mixed with the epoxy resin, and such cationically polymerizable vinyl compounds include styrene, allylbenzene, vinyl ether, N-vinylcarbazole, and N-vinylcarbazole.
- Examples include vinylpyrrolidone.

The photoinitiator used in the present invention which releases a Lewis acid catalyst capable of promoting the polymerization of the cationically polymerizable compound upon irradiation with ultraviolet rays of component B is an aromatic diazonium salt, an aromatic halonium salt, a group Wa or a group VA. Examples include photosensitive aromatic onium salts of group elements.

Such an aromatic diazonium salt has the general formula (1): (
In the formula, R1 and R2 are hydrogen atoms, alkyl groups or alkoxy groups, R3 is a hydrogen atom, an aromatic group or an aromatic group connected by an amide group or a sulfur atom, M is a metal or metalloid, and Q is a halogen atom. and a = (b
-o) holds, and 0 is an integer from 2 to 7 and is equal to the valence of M, and b is an integer greater than C and less than or equal to 8), such as H30. 〇Also, as the aromatic halonium salt, the general formula (n) j
((u+)a (R5).x); (MQg)
(gh) value) (wherein, R4 is a monovalent aromatic organic group, R5 is a divalent aromatic organic group, Metal and Q represent halogen atoms, and d is 0
or 2, e is 0 or 1, and (d+e) is 2
or equal to the valence of
Examples include IIIa P note IP4.

Furthermore, as a photosensitive aromatic onium salt of a Ma group element or a Va group element, the general formula (!10:% formula% (1) (wherein, R6 is a monovalent aromatic organic group, R7 is an alkyl group) is used. , a Schifftetraalkyl group, a monovalent aliphatic group selected from the group consisting of substituted alkyl groups, R8 is a heterocyclic group selected from aliphatic organic groups and aromatic organic groups, or a fused polyvalent organic group, Yke 51Be, % Te M
Group a elements or N SP s As , Sb and B1
M is a metal or metalloid and Q is a halogen atom, 1 is an integer of 0 to 4, j is an integer of 0 to 2, k is an integer of 0 to 2, and (i+j
+k) is equal to the valence of Y, equal to 3 when Y is a group Wa element, equal to 4 when Y is a group V& element, and /=
(m-n) holds, and n is an integer from 2 to 7 and equal to the valence of M, and m is an integer greater than n and less than or equal to 8)
Examples of onium salts of group Ma elements include the following, and examples of onium salts of group VIL elements include O. Mix component B with component A and irradiate it with ultraviolet light. When this is carried out, the B component releases a Lewis acid, and the Lewis acid accelerates the curing of the A component.

The effective addition amount of component B to component A is 0.5 to component A.
-10%, preferably 1-5%. If it is less than 0.5%, the curing speed by ultraviolet irradiation will be slow, and if it exceeds 10%, the manufacturing cost of the marking ink of the present invention will increase, and both are not preferred.

As the pigment (silver) of the component C that can be used in the present invention, there may be mentioned a mixture of a scaly type aluminum powder and a silica powder.

Leafing-type flaky aluminum powder has the property of floating on the surface of the coating film and arranging it in parallel, giving it an excellent shielding effect and a silvery metallic luster. However, when it is used in an ultraviolet curable resin, due to its properties, the ultraviolet rays do not reach the interior of the resin sufficiently, and as a result, only the surface of the coating film is cured, and the curability of the interior of the resin tends to be poor.

In the present invention, by using silica powder together with aluminum powder, when the aluminum powder floats on the coating surface, the silica powder gets between the layers of the aluminum powder, so the aluminum powder is no longer arranged in parallel, and the ultraviolet rays are absorbed by the aluminum powder. It reflects diffusely between the layers and reaches the interior of the resin.

Furthermore, the aluminum powder has a high ultraviolet reflectance and the silica powder has excellent ultraviolet transmittance, which facilitates the ultraviolet rays to reach inside the resin.

Furthermore, in the present invention, by adding component C, the filling rate of aluminum powder and silica powder in the surface layer of the coating film is increased, so that the surface hardness of the coating film is increased and the solvent resistance is significantly improved.

Such leafing type scaly aluminum powder with an average particle size of 10 to 100 μm, and silica powder with an average particle size of 1 to 50 μm can be used in the present invention.

The effective amount of these additives is 5 to 30% for aluminum powder and 1 to 30% for silica powder based on the resin component. If the amount of aluminum powder added is less than 5%, the degree of coloring will be insufficient, and if it exceeds 30%, the ultraviolet curability will be markedly deteriorated due to the shielding effect of the aluminum powder. Furthermore, if the amount of silica powder added is less than 1%, the effect of the combination of silica powder and aluminum powder as described above will be insufficient, and if it exceeds 30%, the adhesion of the cured coating film will tend to deteriorate. ◇ In addition to the above three components, (D) a radical polymerizable compound in an amount of 5 to 50% by weight based on the cationic polymerizable compound of component A having two or more acryloyl groups or methacryloyl groups in one molecule. Compound (hereinafter referred to as
(referred to as component D) and (E) 0.1 to 10 to the radically polymerizable compound.
Weight % radical photosensitizer (hereinafter referred to as component E)
The ultraviolet curability of the marking ink obtained by using the above method can be further improved.

The radically polymerizable compound of component D is a compound having two or more acryloyl groups or methacryloyl groups in one molecule. Examples of such compounds include ethylene glycol di(meth)acrylate, rylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, and 1,6-hexane. Examples include thiol di(meth)acrylate, epoxy(meth)acrylate, trimethylolpropane tri(meth)acrylate, and metaerythritol tri(meth)acrylate, and in the present invention, these may be used alone or as a mixture.

The effective amount of component D added to component A is 5 to 5% relative to component A.
0%, preferably 10-30%. If it is less than 5%, the effect of improving ultraviolet curability will be small, and if it exceeds 50%, the adhesion of the marking ink will tend to decrease.

□The radical photosensitizer used in the present invention as component E must be one that can polymerize the radically polymerizable compound as component D without reducing the photolysis efficiency of component B. For example, benzophenone, benzoin, etc. , thioxanthone, anthraquinone, acetophenone and their derivatives. The effective amount of component E to be added is 0.1 to 10%, preferably 0.5 to 5%, relative to component D.
If it is less than 0.001%, the effect of polymerizing component D will be weak and the curing speed will be slow, and if it exceeds 10%, the photodecomposition efficiency of component B will tend to decrease.

Ultraviolet irradiation is the most efficient means for curing the ultraviolet curable marking ink of the present invention, and examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps. In addition, curing is also possible by irradiation with Muroko radiation.

Furthermore, a viscosity modifier, a rubber plasticizer, a spreading agent, etc. may be added to the marking ink of the present invention within a range that does not deteriorate properties such as ultraviolet curability and solvent resistance.

The marking ink of the present invention has superior adhesion and solvent resistance compared to conventional ultraviolet curable marking inks, and its performance is almost the same as thermosetting marking inks. It can also be applied to areas where high reliability is required, such as marking semiconductor chips, etc., which could not be applied previously.

The present invention will be explained in more detail below based on Examples, but the present invention is not limited only to these Examples.

Example 1 Epicote 82 as a bisphenol A epoxy resin
840 parts mn −2 as epoxidized butadiene resin
7 (manufactured by Nippon Soda ■, trade name) 40 parts and Trimethi 4-
A mixture of 20 parts of 4,4-dimethyldiphenyliodonium hexa7/I/olophosphate and 0.3 parts of anthraquinone is dissolved in a mixture of 20 parts of Rubuvan (reacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). flaky aluminum powder (product name: IPO1 [10
The ultraviolet curable marking ink of the present invention was prepared by mixing and dispersing 20 parts of silica powder (manufactured by Nagashio Ciba Co., Ltd.) and 10 parts of silica powder (manufactured by Nagashio Ciba Co., Ltd.).

The obtained marking ink was marked on the IC chip, and a 2.5 kW high-pressure mercury lamp (product name H254VA, manufactured by Mitsubishi Electric ■) was used as a light source for irradiation at 1'f115 ohm, moving speed 4 m/min, and one irradiation time approximately 1. By irradiating with ultraviolet light for a few seconds, a cured coating with a silvery luster and good appearance was obtained.

The properties of the thus obtained cured coating film were evaluated by the following measurements.

Empi hardness was evaluated by measuring according to the J Engineering S standard. In the Seta tape peeling test, the cured paint film did not peel off at all when the action of applying cellophane tape to the entire surface of the cured paint film and peeling it off was repeated 10 times. ○: Partial peeling: △; Fully peeling: x:

In the trichlene swab rubbing test, a cotton swab impregnated with trichlene was repeatedly rubbed against the surface of the cured coating for one second with a force of 2 to 9 times, and the number of times until the marking became illegible was measured.

The results are shown in Table 1.

Example 2 Araldite 0Y17985 as alicyclic epoxy resin
3 parts of triphenylsulfonium hexafluorophosphate and 0.5 part of diisopropylthioxanthone were dissolved in a mixture consisting of 1 part of pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) and 15 parts of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) to form a floating type. The ultraviolet curable marking ink of the present invention was prepared by mixing and dispersing 20 parts of flaky aluminum powder (trade name 0230T, manufactured by Toyo Aluminum) and 15 parts of silica powder (manufactured by Nagashio Ciba Co., Ltd.).

A cured coating film was prepared in the same manner as in Example 1, and its properties were measured and evaluated. The results are shown in Table 1.

Example 3 DEN 43140 parts as novolac type epoxy resin, Araldite 0Y1794 as alicyclic epoxy resin
2 parts of p-methoxyphenyldiazonium tetrafluoroborate and 1.0 part of benzophenone were dissolved in a mixture consisting of 0 parts of p-methoxyphenyldiazonium tetrafluoroborate and 20 parts of diethylene glycol dimethacrylate (manufactured by Kyoeisha Yushi Kagaku Co., Ltd.). Name 02
The ultraviolet curable marking ink of the present invention was prepared by mixing and dispersing 15 parts of silica powder (manufactured by Nagashio Ciba Co., Ltd.) and 10 parts of silica powder (manufactured by Nagashio Ciba Co., Ltd.).

A cured coating film was prepared in the same manner as in Example 1, and its properties were measured and evaluated. The results are shown in Table 1.

Example 4 Araldite 0Y17940 as alicyclic epoxy resin
Into 0 parts, 2 parts of triphenylsulfonium hexafluoropantimonate was dissolved, and 20 parts of leafing-type flaky aluminum powder (product name P0100, Toyo Aluminum special) and 10 parts of silica powder (manufactured by Nagashio Ciba Co., Ltd.) were added. The ultraviolet curable marking ink of the present invention was prepared by mixing and dispersing. A cured coating film was prepared in the same manner as in Example 1, and its properties were measured and evaluated. The results are shown in Table 1.

Comparative Example 1 50 parts of epoxy acrylate (manufactured by Dainippon Ink & Chemicals, trade name Ullt 8200), polyethylene glycol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name A)
-9() ) 2 parts of benzoin ethyl ether is dissolved in a mixture consisting of 20 parts of hydroxyethyl acrylate and 30 parts of hydroxyethyl acrylate, and leafing type aluminum powder (trade name 0230T, special product of Toyo Aluminum) is dissolved.
A UV curable marking ink was prepared by mixing and dispersing 20 parts.

Thereafter, a cured coating film was prepared and its characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Maleic anhydride 98g (1 mol/l/), phthalic anhydride 14Bg (1 mol), dipropylene glycol 295g
(2 mol) and 0.279 hydride tetraquinone were placed in a Lough flask and stirred while blowing in nitrogen gas.
It was kept at 0°0 for 1 hour. Then, by continuing the reaction at 210°0, an unsaturated polyester having an acid value of 20 was obtained.

In a mixture of 50 parts of the obtained reaction product and 50 parts of hydroxyethyl acrylate, 2 parts of benzoin ethyl ether was dissolved, and further, a flying type aluminum powder (trade name 02!lo'l', manufactured by Toyo Aluminum) was prepared. A cured coating film was prepared and its properties were evaluated in the same manner as in Example 1, in which an ultraviolet curable marking ink was prepared by mixing and dispersing 15 parts. Results first
Comparative Example 3 Commercially available thermosetting marking ink (Markem Inc., #7
224) on the 0 chip, and 150
The properties of the cured coating film obtained by heat curing at °C for 2 hours were evaluated in the same manner as in Example 1. The results are shown in Table 1.

385-

Claims (1)

[Scope of Claims] (1) (A) one or more cationically polymerizable compounds whose main component is an epoxy resin having two or more oxirane rings in one molecule; (B) polymerization of the cationically polymerizable compounds; The effective amount that can liberate the initiable Lewis acid catalyst by ultraviolet irradiation is 0.5 to 10% based on the cationic polymerizable compound.
It is characterized by consisting of leafing type flaky aluminum powder in an amount of 5 to 30% by weight and silica powder in an amount of 1 to 30% by weight based on the resin component as a photoinitiator and (0) pigment in the amount of % by weight. UV-curable marking ink with excellent adhesion and solvent resistance. (2) The photoinitiator is selected from the group consisting of aromatic diazonium salts, aromatic halonium salts, and photosensitive aromatic onium salts of group A or group VA elements, either alone or in a mixture of two or more. The marking ink according to claim (1). (8) (A) one or more cationically polymerizable compounds whose main component is an epoxy resin having two or more oxirane rings in one molecule; (B) a Lewis acid catalyst capable of promoting the polymerization of the cationically polymerizable compound; The effective amount that can be liberated by ultraviolet irradiation is 0.5 to 0.5 to
10% by weight of photoinitiator, (0) glue-fing type flaky aluminum powder in an amount of 5 to 30% by weight based on the resin component as a pigment, and silica powder in an amount of 1 to 30% by weight, (D ) A radically polymerizable compound in an amount of 5 to 50% by weight based on the cationically polymerizable compound having two or more acryloyl groups or methacrytetrayl groups in one molecule; Ultraviolet curable marking ink with excellent adhesion and solvent resistance characterized by comprising ~10% by weight of a radical photosensitizer. (4) The photoinitiator is aromatic diazonium salt, aromatic halonium The marking ink according to claim (3) is a marking ink 0 ( 5) Claim 3, wherein the radical photosensitizer is selected from the group consisting of benzophenone, benzoin, thioxanthone, anthraquinone, acetophenone, and derivatives thereof, either alone or as a mixture of two or more thereof. marking ink.