KR0182828B1 - Anti-flammable thin core resin composition for the usage of automatic test by fluorescence detection - Google Patents

Abstract

The present invention is a resin composition for flame-retardant copper foil laminates for fluorescence detection type automatic visual inspection comprising a trifunctional epoxy resin containing bromine, a benzophenone-based or a benzotriazole-based UV stabilizer, a pyrazoline-based fluorescent dye, a curing agent, and a curing accelerator.

Description

Resin composition for flame retardant copper clad laminate for fluorescence detection method

The present invention relates to a method of manufacturing a high heat resistant copper clad laminate used for automatic visual inspection using a fluorescence detection method having ultraviolet shielding function and flame retardancy.

The thin core copper core laminate (Thin core) used for multilayer circuit boards among copper foil laminates is formed through several achievements in order to form a multilayer circuit board. Therefore, a considerable thermal change is made, thus forming a thin copper laminate plate for core materials. It requires high heat resistance and high glass transition temperature as its characteristic value.

In the case of such a lack of heat resistance, during the manufacture of multilayer printed circuit boards, the thermal phenomenon such as lead treatment (above 260 ℃) is caused by hot thermal shocks, and the chip is mounted after completion of the circuit due to thermal expansion due to thermal change. The misalignment of the holes (Hole) causes a defect that becomes impossible to use.

In addition, there is a problem of introducing an automatic visual inspection device when inspecting a multilayer circuit board. In general, an automatic visual inspection method is divided into two types in a manufacturing process of a printed circuit board.

Conventional inspection method is applied to a method of inspecting the pattern of the circuit by detecting the intensity of the reflected light by irradiating the white light to the substrate, which is applied to the irradiation of light after etching the substrate (Etching) It is based on the principle that light is strongly reflected on the metal surface and light is weakly reflected on the etched insulating layer.

However, since this method uses strong light, there is a high possibility of damage on the metal surface, and in the case of applying a resin for circuit formation on the substrate or applying solderresist ink during the whole process to lead after etching. There is a disadvantage that the reflected light from the surface is strong and difficult to distinguish from the reflected light on the metal surface.

In particular, this method has a disadvantage in that inspection becomes poor as the circuit of the circuit on the back surface of the surface to be inspected is reflected as the substrate becomes thinner.

Therefore, in recent years, an automatic visual inspection method using fluorescence is gradually increasing, which is generated from organic substances such as image forming resins of insulating layers of copper-clad laminates by irradiating light of low specific wavelength (typically 400 to 600 nm) onto the substrate. It is a method of inspecting the appearance by detecting fluorescence of a specific wavelength.

In particular, this method is highly accurate and there is no problem appearing in the existing method is expected to be used a lot in the future is a situation that is absolutely required, especially in the copper clad laminate for the core material used in the multilayer board.

For the automatic visual inspection method of the fluorescence detection method, the insulating layer should have a function of displaying fluorescence. Since the detection method cannot be used with a conventional copper clad laminate, a special function should be given.

In general, when forming a circuit for manufacturing a multilayer printed circuit copper foil laminated plate to prevent the lead from soldering (Soldering), the photosensitive film or photosensitive ink is applied to the substrate and then cured with ultraviolet rays. In the case of exposure, ultraviolet rays harden the photosensitive film or ink on the back surface through the base of the copper-clad laminate to form an afterimage, which causes a problem.

Therefore, in order to solve such a problem, a method of providing an ultraviolet shielding function to the photosensitive ink itself or a method of providing an ultraviolet shielding function to the substrate itself of the copper-clad laminate is used. The former method provides a function because the thickness of the ink is thin. In the case of a multilayer printed circuit board, the latter method is widely used because there is a disadvantage in that the effect is remarkably deteriorated.

As the latter method, a method of dispersing an inorganic filler (TiO ₂ ) is shown in Japanese Patent Application Laid-Open No. 2-219642. However, the method of dispersing such an inorganic filler becomes an opaque laminate, which is an inner layer of a copper clad laminate, and is rather irradiated by an inorganic filler. This scattering problem may occur.

As another method, a method of using a benzophenone-based or a benzotriazole-based ultraviolet stabilizer as a method of adding an ultraviolet stabilizer is disclosed in Japanese Patent Application Laid-Open No. 2-198189, No. 63-289986, and alkyl thioxanthone. -thioxanthone) is described in Japanese Patent Laid-Open No. 2-227442.

However, this method has only the effect of shielding ultraviolet rays below 400 nm, has no fluorescence effect, and has the disadvantage that the color of the copper clad laminate is significantly discolored.

Therefore, the present invention solves these problems, etc.

1) High Tg characteristics,

2) Fluorescence emitting function corresponding to automatic visual inspection device for fluorescence method,

3) UV shielding function

4) Flame retardant (94VO level)

The present invention relates to the production of a resin composition used for producing a thin copper clad laminate used as a core material, especially for a high-functional copper clad laminate having the same.

Hereinafter, the present invention will be described in detail as follows.

The present invention is 100 parts by weight of the trifunctional epoxy resin containing bromine, 0.1 to 4.0 parts by weight of benzophenone or benzotriazole-based UV stabilizer, 0.005 to 3.0 parts by weight of parazoline-based fluorescent dye, 1.0 to 30 dicyanodiamide as a curing agent Flame-retardant copper foil for automatic detection of fluorescence detection method characterized in that it consists of a catalytic amount of one or two or more mixtures selected from PHR, 2-methylimidazole, 2-ethyl-4-methylimidazole, and benzimidazole as a curing accelerator. It relates to a resin composition for laminated plates.

Hereinafter, the present invention will be described in more detail.

The trifunctional epoxy resin containing bromine in the present invention is represented by the following formula (2), the epoxy equivalent of 300 to 1,000, the bromine content of 16 to 30% as a basic composition of the resin composition.

UV stabilizers include benzophenone and benzotriazole-based, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2 -Hydroxy-4-n-dodecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 Benzophenone-based ultraviolet absorbers such as -hydroxy-4-benzyloxybenzophenone, 2- (2-hydroxy-5'-methylphenyl) benzotriazole, and 2- (2-hydroxy-3,5-di-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'- Benzotriazole type ultraviolet absorbers, such as t-butyl-5'-methylphenyl) benzotriazole, are used.

The amount used is 0.1 to 4.0 parts by weight based on 100 parts by weight of the trifunctional epoxy resin containing bromine. When less than 0.1 is used, the UV shielding effect is insignificant. In addition to this, there is a disadvantage that the color of the copper clad laminate laminate becomes worse and the heat resistance is somewhat reduced.

In addition, the benzotriazole type is more suitable than the benzophenone type because the ultraviolet absorption at the wavelength of 300 to 400 nm is better.

Pyrazoline-based fluorescent dye is a compound represented by the following formula

In general, when irradiated with light of 400 ~ 650nm it emits a fluorescence of less than 800nm.

Particularly, pyrazoline-based fluorescent dyes have the function of absorbing ultraviolet rays in the ultraviolet region of 200 to 420 nm (maximum absorption wavelength 370 nm). ) Shows the effect of shielding against ultraviolet rays, and also reinforces the existing absorption zone.

When the amount is used, 0.005 to 3.0 parts by weight based on 100 parts by weight of trifunctional epoxy resin is used. When the amount is less than 0.005 parts by weight, the amount of fluorescence emitted may be small, which may cause an error. There is a problem that the physical properties of the copper-clad laminate, such as a large rise and the heat resistance is reduced as the fluorescent material is added.

Curing agent uses dicyanoodiamide (Dicyanodiamide) 1.0 ~ 30PHR, when using less than 1.0 PHR, the amount of the curing agent is small, so the complete curing is not achieved, significantly lower the physical properties. Since the agent remains in the state of a monomer, there is a disadvantage in that physical properties are lowered rather than using an appropriate amount of a curing agent.

The hardening accelerator is used alone or in combination of 2-methylimidazole, 2-ethyl-4-methylimidazole and benzimidazole which are imidazole-based curing accelerators, and a catalytic amount is used.

Since it is a curing accelerator to promote the reaction, it can be controlled according to the manufacturing conditions of the copper-clad laminate, and when using too much, it is difficult to control the reaction, and the cost of the curing agent hinders the reaction and the cost is increased.

The effect of the present invention is to give a fluorescent light emitting function to the existing FR-4 for the flame-retardant printed circuit by manufacturing a copper-clad laminate that can be used for automatic appearance inspection using fluorescence and applied to automatic appearance inspection printed circuit board Increasing the inspection efficiency, it has the effect of reducing the defect rate of the printed circuit board, improving the productivity by shortening the inspection time, and making it possible to inspect what was difficult in the automatic external inspection method using conventional light reflection. By giving the function, the ultraviolet ray reaches the back side when curing the solder ink using ultraviolet rays, and it has the effect of UV shielding copper clad laminate to remove the afterimage defect caused by curing the part outside the circuit as well as the existing benzophenone And ultraviolet light not shielded from benzotriazole It has the effect of amplifying its function by shielding a wide area.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

2.5 g of dicyanodiamide was added to 20 g of N, N'-dimethylformamide and completely dissolved. 0.15 g of 2-methylimidazole and 15 g of methyl cellosolve were added thereto, followed by stirring to completely dissolve it. )

Ultra super stabilizer 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole (tinuvin 326, Ciba-Geigy) 0,2 g and fluorescent dye Neo Super HR-21 0.05 g of Japan Central Synthetic Chemicals was completely dissolved in 20 g of acetone.

After adding (Solution 2) to (Solution 1) and stirring for 10 minutes, mix thoroughly after adding 100g of VF2802M75 trifunctional epoxy resin (Epoxy equivalent 375, Bromine content 25%, product of Nippon Samjung Petrochemical) Stirring to prepare a resin composition.

The resin composition prepared as described above was impregnated into glass fibers and then dried by hot air to prepare a prepreg having a resin content of 43% by weight. The two prepregs were laminated, and then laminated with copper foil having a thickness of 18 μm on both sides, and then heated and pressed for 90 minutes at a temperature and pressure of 180 ° C. and 40 kg / cm ² using a press to press a copper foil laminated plate having a thickness of 0.4 mm. Prepared. The copper foil laminate was etched using an etching solution, and then the amount of fluorescence was measured using an OPVISTECH (USA) VISION-206 automatic visual inspection device. The UV shielding rate was measured using a high pressure mercury lamp (wavelength 300 ~ 400nm, 1kW). Was irradiated with a light amount of 700mj and the degree of transmission thereof was measured with a photometer.

Example 2

Neo Super HR-21 of (Solution 2) of Example 1 was used in an amount of 0.1 g instead of 0.05 g.

Example 3

Neo Super HR-21 of (Solution 2) of Example 1 was increased to 0.2 g instead of 0.05 g, and the other procedures were carried out in the same manner.

Example 4

Instead of 0.2 g of Tinuvin 326 of Example 1 (Solution 2), the amount was increased to 0.4 g, and the other procedures were carried out in the same manner.

Comparative Example 1

YDB424A80 (Epoxy equivalent 400, Kukdo Chemical Co., Ltd.) was used in place of the VF2802M75 resin of Example 1, and the other procedures were carried out in the same manner.

Comparative Example 2

Other than (Solution 2) of Example 1 was carried out in the same manner.

Comparative Example 3

Of the (Solution 2) of Example 1, except that Neo Neo HR-21 was not used, the same procedure was followed.

Claims (1)

100 parts by weight of trifunctional epoxy resin represented by the following formula 2 containing 18 to 30% bromine and an epoxy equivalent of 300 to 1,000, 0.1 to 4.0 parts by weight of a benzophenone or benzotriazole-based UV stabilizer, and pyra represented by the following formula 1 0.005 to 3.0 parts by weight of a sleepy fluorescent dye, one or two or more selected from dicyanodiamide 1.0 to 30 PHR as a curing agent, 2-methylimidazole, 2-ethyl-4-methylimidazole, and benzimidazole as a curing accelerator. A resin composition for flame-retardant copper-clad laminate for fluorescence detection type automatic visual inspection, comprising a catalytic amount of a mixture.