KR20110116451A - (meth)acryl modified polyurethane, photocurable composition for discoloration comprising the same, and a method for determining quality of photocurable compositions by the change of the compostion's color during photocuring - Google Patents

Abstract

The present invention relates to a method for changing the color before and after curing during photocuring of the photocurable resin composition, and a method for managing the quality of the photocurable resin through such color change before and after curing.
The method for changing the color before and after curing according to the present invention is to use irreversible photochromic dye or reversible photochromic dye in photocurable urethane-modified (meth) acrylate, carbonate-containing urethane-modified urethane-modified (meth) acrylate resin to be irreversible conditions. The method of controlling the quality of the photocurable resin by changing the color before and after curing according to the present invention includes determining the abnormality of the curing equipment or the degree of curing of the resin by only changing the color when coating the electrode protective material in a module process such as LCD. It is characterized in that it is given a significant advantage in quality control.
When applying the technology of the present invention to the existing photo-curable electrode protective moisture-proof insulation coating, the physical properties such as curing speed, adhesive strength, etc. are maintained at the same level, and color and density of the color change depending on the degree of curing, so that quality control can be visually checked. Therefore, not only the convenience of work but also the effect of giving the concealment power is also brought together.
The method of changing the color before and after curing during photocuring of the photocurable resin composition according to the present invention, and the method of managing the quality of the photocurable resin through the color change before and after curing is a liquid crystal display device, a plasma display device, an organic light emitting diode It can be used in the field of moisture-proof protection agent, such as electrode protection agent of flat panel displays, capacitor | condenser of electronic products, etc.

Description

(Meth) acrylic modified urethane resin, photocurable discoloration resin composition comprising the same, and a method of measuring the quality of the photocurable composition by changing the color before and after curing the photocurable composition photocurable {(Meth) acryl modified polyurethane, photocurable composition for discoloration comprising the same, and a method for determining quality of photocurable compositions by the change of the compostion's color during photocuring}

The present invention provides a color before and after photocuring by introducing a photochromic dye into a urethane-modified (meth) acrylate, a carbonate group-induced urethane-modified (meth) acrylate, or a silicone-induced urethane-modified (meth) acrylate, which is a conventionally known photocurable compound. It relates to a photocurable discoloration resin composition capable of implementing a change.

The present invention also relates to a method of changing the color before and after curing during photocuring of the photocurable resin composition, and a method of measuring the quality of the photocurable resin through such color change before and after curing.

The present invention also relates to a novel (meth) acrylic modified urethane resin that can be used in the photocurable discoloration resin composition or the above methods.

In recent years, electric devices are lighter and more multifunctional each year, and components and electrodes in the product tend to be densely and highly integrated. Therefore, printed circuit boards mounted on various electric devices that control them are very sensitive to the external environment, which may cause problems. I'm going. Therefore, an insulation treatment is performed for the purpose of protecting the printed circuit board from an external environment such as moisture, shock, gas, or the like. In this insulation treatment, it is widely used to coat protective coatings with acrylic resins, urethane resins, silicone moisture curable resins, epoxy thermosetting resins, etc.However, acrylic resins and urethane resins are dissolved in an organic solvent and then dried. It is generally performed as a method of forming a coating film for the final purpose. Since this type of moisture-proof insulating coating agent releases organic solvents into the atmosphere during painting, there is a disadvantage of high environmental load due to air pollution. The risk of fire from organic solvents is also high. On the other hand, in the case of silicone moisture curable resins and epoxy thermosetting resins, the time required for curing decreases from minutes to hours, and the silicone moisture curable adhesives have lower crosslinking densities in the silicone structure than light (ultraviolet) curable resins and epoxy series. Curing resin has a disadvantage that the moisture permeability is high due to a large amount of polar functional groups by curing.

As another method, the method of preparing UV-curable adhesives by attaching acrylic functional groups to both ends of extremely low polar oligomer diols of Japanese Patent Application Laid-Open Nos. 10-95967 and 2004-107602 is excellent in moisture resistance and productivity. The adhesive force to the polyimide film used for the electrode part of a component is low, and there exists a problem of inferior adhesiveness.

As another method, the urethane (meth) acrylate-based UV-curable adhesive of Korean Patent Application No. 10-2005-000327 has excellent adhesion to polyimide film or glass, but moisture penetrates under high temperature and high humidity. When used in integrated electronic products by forming a moisture band between the adhesive and the adhesive is an important cause of short circuit phenomenon.

Recently, researches on electrode protective coatings using photo (ultraviolet) curable resins incorporating photocurable monomers into (meth) acrylic modified resins have been actively developed and widely expanded in actual processes. Although it is applied, urethane-modified acrylic resins, which have been used as an electrode protection agent until now, such as Japanese Patent Application Laid-Open No. 2006-89627 and Korean Patent 10-0910184, are hard to distinguish visually before and after photocuring and are hardened by pricking them with a stick. There is a hassle to judge whether or not.

Therefore, in order to solve these problems, by giving the characteristics that the color before and after the curing of the photocurable resin, it is possible to confirm whether the curing only by changing the color, it is desired to develop a new concept of electrode protective agent with increased convenience of quality control. .

The technical problem to be achieved by the present invention is to achieve a high curing rate compared to the conventional epoxy thermosetting and silicone moisture curing type, and to manufacture a photo-curable resin composition that maintains excellent moisture-proof insulation and adhesive strength with little organic material emission, It is intended to improve durability by applying to electrodes and capacitors of electronic products and protecting it from the external environment.

In addition, the technical problem of the present invention is to maintain the advantages of the existing photo-curable resins, the quality control that it is difficult to determine the presence or absence of the curing of the existing products before and after the application when applied to the electronic component manufacturing process In order to solve the difficulties, it is intended to dramatically improve the convenience of quality control by giving clear color change before and after curing.

In particular, it is an object of the present invention to provide a photocurable resin composition capable of implementing color changes before and after photocuring, while maintaining the advantages of conventional resins such as excellent moisture-proof insulation and adhesion, fast curing, environmental load reduction, thereby In addition to achieving the original purpose of the coating agent, moisture-proof insulation of electrodes, capacitors, etc. to be used, it has the advantage of quality control by color change, not only providing breakthrough convenience in quality control field, but also concealment and appearance of the product. I want to give it a beauty.

The present invention also provides a highly reliable electronic component insulated using the light (ultraviolet) curable moisture proof insulating coating agent for a printed circuit board.

The present invention provides a color before and after photocuring by introducing a photochromic dye into a urethane-modified (meth) acrylate, a carbonate group-induced urethane-modified (meth) acrylate, or a silicone-induced urethane-modified (meth) acrylate, which is a conventionally known photocurable compound. It provides a photocurable discoloration resin composition which can implement a change.

The present invention is also a novel urethane modification, which may be used instead of the urethane-modified (meth) acrylate, the carbonate group-introduced urethane-modified (meth) acrylate, or the silicone-introduced urethane-modified (meth) acrylate, which are conventionally known photocurable compounds. Regarding (meth) acrylate, the urethane-modified (meth) acrylate is an isocyanate in a molecule of a diol compound having a molecular weight of 200 or less and a diol compound having a molecular weight of 1,000 to 3,000 using a diluent having a urethane ethylenically unsaturated double bond. A urethane compound is prepared by reacting with an excess of a diisocyanate compound having two groups, and reacting a compound having one group selected from a hydroxyl group, an amine group or a carboxyl group in one molecule with an ethylenically unsaturated compound having two carboxyl groups. Are manufactured.

The present invention provides a color before and after photocuring by introducing a photochromic dye into a urethane-modified (meth) acrylate, a carbonate group-induced urethane-modified (meth) acrylate, or a silicone-induced urethane-modified (meth) acrylate, which is a conventionally known photocurable compound. It provides a way to change. In detail, the method for changing the color before and after curing according to the present invention is irreversible conditions for irreversible photochromic dye or reversible photochromic dye in photocurable urethane-modified (meth) acrylate, carbonate-introduced urethane-modified (meth) acrylate resin The method of controlling the quality of the photocurable resin through the color change before and after curing according to the present invention includes the abnormality of the curing equipment or the degree of curing of the resin by only changing the color when coating the electrode protective material in a module process such as LCD. It can be judged that it is characterized by a breakthrough advantage in quality control.

The photocurable discoloration resin composition according to the present invention can easily grasp the degree of curing by the color change before and after photocuring to provide convenience in quality control when manufacturing electronic components, it is very effective in reducing defect rate and improving production efficiency.

The photocurable resin composition and method of the present invention has an advantage in that quality control is possible only by changing the color by applying a color change according to the degree of curing. That is, according to the present invention, since the ultraviolet rays are irradiated from the transparent or semi-transparent color before curing, the unique color appears as the curing proceeds, so that the degree of curing can be grasped only by the color, thereby providing convenience in quality control in manufacturing electronic components. It is also very effective in reducing defective rate and improving production efficiency. In addition, in the quality measurement method according to the present invention, since the color is initially expressed as the curing proceeds in a transparent or translucent form, the color of light due to the pigment having a color development characteristic from the initial stage or the pigment particle when the dye is used. There is an advantage that does not cause problems such as a decrease in the amount of energy reached by the light source due to the energy absorption of the blocking color dye, a decrease in the curing effect due to the energy absorption of the color itself.

In addition, the composition and method according to the present invention contribute to providing a highly reliable electronic component moisture-proof insulation treatment with a photo-curable moisture-proof insulating coating, an electrode such as a highly integrated liquid crystal display device, a plasma display device, an organic light emitting diode, It is particularly useful when used as a moisture proof protective coating adhesive for condensers.

The (meth) acryl-modified urethane resin according to the present invention has an advantage of easy coloration compared to conventional resins. In addition, the light (ultraviolet) curable resin composition containing the resin has a very low generation of volatile organic solvents during curing, so that the environmental load is low, the moisture permeability is very low, and has sufficient adhesion to the substrate material.

EMBODIMENT OF THE INVENTION Hereinafter, the (meth) acryl modified urethane resin, the photocurable discoloration resin composition, the photocurable moisture proof insulating coating agent for printed circuit boards, an electronic component, and its manufacturing method which concern on this invention are demonstrated in detail according to embodiment. However, the present invention is not limited to this embodiment.

The present invention relates to a method for changing the color before and after curing during photocuring of a photocurable resin composition, comprising mixing a photocurable resin composition and a photochromic dye. The photochromic dye is one from the group consisting of 4,4 ', 4 "-methylidritris (N, N-dimethylaniline), a spiroxazine photochromic dye, a naphthopyranic photochromic dye, and derivatives thereof Or two or more kinds may be selected.

The photocurable resin composition may include a photocurable oligomer compound, a photopolymerizable monomer, and a photopolymerization initiator.

When the total amount of the photocurable oligomer compound and the photopolymerizable monomer was 100 parts by weight, 0.1 to 10 parts by weight of the photochromic dye, 20 to 60 parts by weight of the photocurable oligomer compound, 40 to 80 parts by weight of the photopolymerizable monomer, It may be included in 1 to 10 parts by weight of the photopolymerization initiator. The photocurable oligomer compound may be a urethane-modified (meth) acrylate, a carbonate-group-introduced urethane-modified (meth) acrylate, or a silicone-introduced urethane-modified (meth) acrylate. The method may further comprise adding an ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms for vivid color development.

The ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group may be selected from the group consisting of acrylic acid, (meth) acrylic acid, itaconic acid and fumaric acid, but is not limited thereto.

The saturated fatty acid having 8 or more carbon atoms may be selected from the group consisting of stearic acid, isononanoic acid and dodecylbenzenesulfonic acid, but is not limited thereto.

The amount of the ethylenically unsaturated double bond compound having a hydroxyl group or carboxyl group or a saturated fatty acid having 8 or more carbon atoms is based on 100 parts by weight of the photocurable resin composition (wherein 100 parts by weight is with or without photochromic dye). 0.1 parts by weight to 5.0 parts by weight.

The present invention also relates to a method for measuring the quality of a product containing the resin by using a color change before and after curing during photocuring of the photocurable resin composition.

The photocurable resin composition is characterized by containing a photochromic dye.

The present invention also relates to irreversible irreversible photochromic dyes or reversible photochromic dyes to at least one of photocurable urethane modified (meth) acrylates, carbonate group-introduced urethane-modified (meth) acrylates and silicone-introduced urethane-modified (meth) acrylates. A method of changing the color before and after curing, including use under conditions.

The irreversible conditions are conditions in which an ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms is added.

The ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group may be selected from the group consisting of acrylic acid, (meth) acrylic acid, itaconic acid and fumaric acid, but is not limited thereto.

The saturated fatty acid having 8 or more carbon atoms may be selected from the group consisting of stearic acid, isononanoic acid and dodecylbenzenesulfonic acid, but is not limited thereto.

The amount of the ethylenically unsaturated double bond compound having a hydroxyl group or carboxyl group or a saturated fatty acid having 8 or more carbon atoms is based on 100 parts by weight of the photocurable resin composition (wherein 100 parts by weight is with or without photochromic dye). 0.1 parts by weight to 5.0 parts by weight.

The photocurable discoloration resin composition according to the present invention includes (A) a photochromic dye; (B) photocurable oligomeric compounds; (C) photopolymerizable monomers; (D) photoinitiator; And (E) additives.

When the total amount of the (B) photocurable oligomer compound and (C) the photopolymerizable monomer is 100 parts by weight,

(A) 0.1 to 10 parts by weight of the photochromic dye;

(B) 20 to 60 parts by weight of the photocurable oligomeric compound;

(C) 40 to 80 parts by weight of the photopolymerizable monomer;

(D) 1-10 weight part of photoinitiators; And

(E) 0.1 to 7 parts by weight of the additive may be included.

(A) the photochromic dye is a group consisting of 4,4 ', 4 "-methylidinetris (N, N-dimethylaniline), spiroxazine photochromic dyes, naphthopyran-based photochromic dyes and derivatives thereof It may be selected from one or two or more from.

The said (B) photocurable oligomer compound is 1 type, or 2 or more types from the photocurable resin of a urethane modified (meth) acrylate, a carbonate group-introduced urethane-modified (meth) acrylate, or a silicone-introduced urethane-modified (meth) acrylate. Can be selected.

Monofunctional acrylate which the said (C) photopolymerizable monomer compound has a hydroxyl group of (c1) polarity; (c2) linear monofunctional acrylate having no polar functional group; (c3) photopolymerizable monomers having an ethylenically unsaturated double bond and a cyclic aliphatic group; And (c4) a polyfunctional acrylate having 2 to 5 acrylic functional groups.

0.1 to 5 parts by weight of a monofunctional acrylate having a hydroxyl group of (c1) polarity, based on a total of 100 parts by weight of the component (B) and (C); (c2) 1 to 10 parts by weight of a monofunctional acrylate having a linear structure having no polar functional group; (c3) 20 to 60 parts by weight of a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group; And (c4) 2 to 15 parts by weight of a multifunctional acrylate having 2 to 5 acrylic functional groups.

The (D) photopolymerization initiator may be selected from the group consisting of carbonyl photopolymerization initiator, sulfide photopolymerization initiator, quinone photopolymerization initiator, azo photopolymerization initiator and peroxide photopolymerization initiator.

The additive component (E) may be selected from the group consisting of a polymerization inhibitor, acryloylmorphine and a silane coupling agent, and saturated fatty acids having 8 or more carbon atoms, or two or more thereof.

Photocurable discoloration resin composition according to the invention is It may further include an ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms. The ethylenically unsaturated double bond compound having the hydroxyl group or carboxyl group may be selected from the group consisting of acrylic acid, (meth) acrylic acid, itaconic acid and fumaric acid. The saturated fatty acid having 8 or more carbon atoms may be selected from the group consisting of stearic acid, isononanoic acid and dodecylbenzenesulfonic acid.

0.1 parts by weight to 5.0 parts by weight, preferably 0.3 parts by weight to 4.0 parts by weight, based on 100 parts by weight of the ethylenically unsaturated double bond compound having 8 or more carbon atoms having a hydroxyl group or carboxyl group, or a saturated fatty acid having 8 or more carbon atoms. It may be wealth.

The present invention also provides a photocurable discoloration coating agent for a printed circuit board containing the above-mentioned photocurable discoloration resin composition. The present invention relates to an electronic component insulated with the photocurable discoloration coating agent for a printed circuit board. The present invention also relates to a method for producing an electronic component, wherein the photocurable discoloration resin composition is applied to an electronic component and cured.

The (meth) acryl-modified urethane resin which can be used in the photocurable discoloration resin composition according to the present invention includes (b1) diol compounds having a number average molecular weight of 200 or less, (b2) diol compounds having a number average molecular weight of 1,000 to 3,000, (b3) 1 To a urethane compound prepared by first copolymerizing a diisocyanate compound having two or more isocyanate groups in a molecule with (b4) a monofunctional diluent capable of photopolymerization as a solvent, (b5) one of a hydroxy group, an amine group and a carboxyl group The branch is obtained by mixing and reacting a (meth) acrylate monomer having a number average molecular weight of 300 or less and an ethylenically unsaturated compound having two carboxyl groups in one molecule of (b6).

The diol compound having a molecular weight of 200 or less (b1) has a structure of Formula 1, and the amount of the diol compound used may be 0.5 to 0.8 equivalent ratio of the compound (b1) when the diisocyanate group is 1 equivalent. .

[Formula 1]

HO- (R ₁ ) -OH

Wherein R ₁ is a saturated or unsaturated group consisting of only 2 to 12 carbon atoms and a hydrogen atom.

(b2) The diol compound having a molecular weight of 1,000 to 3,000 is selected from the group consisting of polyethylenediol, polypropylenediol, polyisoprendiol, hydrogenated butadienediol, poly (ethylene-co-butylene) diol, polytetramethylene glycol and polybutenediol When 1 type, or 2 or more types are selected and the usage-amount of (b2) component makes 1 equivalent of (b3) diisocyanate group, a hydroxyl group can be used in 0.1-0.5 equivalent ratio.

(b3) Compounds having two or more isocyanate groups in one molecule include toluene-2,4-diisocyanate, 1,6-hexamethylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate and iso One or two or more selected from the group consisting of phorone diisocyanate, trimethylhexamethylene diisocyanate and hydrogenated compounds thereof, and the amount of the component (b3) is used in the total hydroxyl group equivalents of the compound used as the component (b1) and (b2) The diisocyanate group equivalent of component (b3) may be used in an amount of 0.1 to 1.0 equivalents more.

(b4) The photopolymerizable monofunctional diluent may be a (meth) acrylate compound having a linear or cyclic aliphatic structure having no ethylenically unsaturated double bond represented by the formula (2) without having a polar functional group such as a hydroxyl group, an amine group or a carboxyl group. .

[Formula 2]

H ₂ C = CHR ₁ -COO-R ₂

Where

R ₁ is hydrogen or CH ₃ , and R ₂ is an alkyl structure having a linear or cyclic aliphatic structure composed of only 1 to 12 carbon atoms and hydrogen.

The component (b5) is 2-hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, diethylaminoethyl (meth) acrylate. With dimethylaminomethyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid and 2- (meth) acryloyloxyethyl maleic acid It may be selected from the group consisting of, and the component (b6) may be selected from the group consisting of itaconic acid and fumaric acid.

At least one of the above components (b5) and at least one of the above components (b6) are mixed and used, and the amount of each component used is higher than that of the unreacted diisocyanate group equivalent of the component (b3) and (b5) and (b6). The hydroxy group, amine group or carboxyl equivalents sum of the components may be combined in amounts of 0.1 to 0.5 equivalents.

The number average molecular weight of the (meth) acryl-modified urethane resin according to the present invention may be 5,000 to 40,000.

[Light (Ultraviolet) Curable Discoloration Resin Composition]

The method according to the present invention is characterized by adding a photochromic dye to a conventional photocurable resin compound. In detail, the method according to the present invention comprises: (B) a photocurable oligomeric compound; (C) photopolymerizable monomers; (D) photoinitiator; And (E) mixing the photocurable resin composition of the additive component with the (A) photochromic dye. When each component is 100 parts by weight of the total of the (B) photocurable oligomer compound and (C) photopolymerizable monomer,

(A) 0.1 to 10 parts by weight of the photochromic dye;

(B) 20 to 60 parts by weight of the photocurable oligomeric compound;

(C) 40 to 80 parts by weight of the photopolymerizable monomer;

(D) 1 to 10 parts by weight of the photopolymerization initiator; And

(E) 0.1 to 7 parts by weight of the additive may be included.

Hereinafter, each component is demonstrated.

[Component (A)]

As the (A) photochromic dye component, both reversible or irreversible photochromic dyes can be used, but irreversibility is more preferable in terms of maintaining color identity. Examples include 4,4 ', 4 "-methylidritris (N, N-dimethylaniline) and spiroxazine photochromic dyes, naphthopyran photochromic dyes and derivatives thereof, more specifically 4 1 type or 2 or more types of photochromic dyes, such as 4 ', 4 "-methylidritris (N, N- dimethylaniline), photochromic blue, photochromic red, photochromic violet, and photochromic yellow It can be used in combination, but is not limited thereto.

The present invention is designed to give a color change according to the degree of curing, so that quality control is possible only by color, which is a unique color appears as the curing proceeds by irradiating ultraviolet rays in a transparent or semi-transparent color before curing. In order to prevent the color from being reversibly returned when the ultraviolet rays are removed, it is possible to use irreversible dyes, or when using the reversible dyes, when preparing the hydroxyl group or the carboxyl group during the photocurable discoloration resin composition. Or by introducing a small amount into the photocurable monomer composition.

That is, by controlling the irreversible photochromic dye and the irreversible photochromic dye in an irreversible environment, the color developed after curing is not returned to the original color. In the case of the type dye, the developed color disappears when the light source is removed, whereas in the present invention, as the curing proceeds in a transparent or semi-transparent form, the color is expressed and the expressed color remains the color even when the light source is removed. This has the advantage that quality control can be done by color change.

In the case of existing pigments or dyes, the initial color is also given, so that the energy of the light source used for curing is lowered to reach the core due to the blocking of light by the pigment, and the color of the dye itself is absorbed. While uncured is highly likely to occur due to a decrease in curing effect due to energy reduction required for curing due to energy absorption due to wavelengths, the present invention initially overcomes this disadvantage because of its transparent form.

The component (A) used in the present invention uses 0.1 to 10 parts by weight based on 100 parts by weight of the total of the following components (B) and (C), preferably 0.1 to 1.5 parts by weight. If the amount is less than 0.1 parts by weight, it is difficult to achieve the desired color after curing, and if it exceeds 10 parts by weight, the problem of increasing the initial color and hardening force tends to cause surface adhesion.

[Component (B)]

As the photocurable oligomer component (B), a conventionally known photocurable oligomer resin may be used, and the photocurable oligomer resin is not particularly limited, and those skilled in the art will be able to prepare the photocurable oligomer resin by a known method if necessary.

Examples of the photocurable oligomer component include urethane-modified (meth) acrylates, carbonate-group-introduced urethane-modified (meth) acrylates, and silicone-introduced urethane-modified (meth) acrylates.

Examples of urethane-modified (meth) acrylates include, but are not limited to, those described in Japanese Patent Application Laid-Open No. 2006-89627, Japanese Patent Application No. 2008-291114, and Japanese Patent Application No. 2008-280414.

Although the photocurable oligomer resin known as (B) component can be used, Preferably, the urethane modified (meth) acrylate which concerns on this invention can be used.

The urethane-modified (meth) acrylate according to the present invention is (b1) diol compound having a number average molecular weight of 200 or less (b2) diol compound having a number average molecular weight of 1,000 to 3,000 (b3) diisocyanate compound having two isocyanate groups in 1 molecule (B4) was first copolymerized with a photopolymerizable monofunctional diluent as a solvent to prepare a urethane compound, wherein (b5) a number average molecular weight of 300 or less (meth) having one group selected from among hydroxy, amine or carboxyl groups in one molecule It can be obtained by mixing and reacting an acrylate monomer and the ethylenically unsaturated compound which has two carboxyl groups in 1 molecule (b6).

Examples of the carbonate group-introduced urethane-modified (meth) acrylate include, but are not limited to, those described in Japanese Patent Application Laid-Open No. 2006-45341 and Japanese Patent Application Laid-Open No. 2007-314768.

Examples of silicone-introduced urethane-modified (meth) acrylates include, but are not limited to, those described in Japanese Patent Application Laid-Open No. 2007-308680. These patent documents are incorporated herein by reference in their entirety.

In the case of irreversible dyes, the color shade of color is generally changed according to the content of photochromic dyes, but in the case of reversible dyes, photocurable compounds are manufactured or marketed to solve the problem of color returning after the light source is removed. An ethylenically unsaturated double bond compound having a trace hydroxyl group or carboxyl group may be added to the oligomer product, or a trace amount of saturated fatty acid having 8 or more carbon atoms may be added. The addition amount can be adjusted according to the desired color development degree, and the smaller the addition amount, the lighter or lighter the color after the final curing appears. Examples of the ethylenically unsaturated double bond compound that may be added include acrylic acid, (meth) acrylic acid, itaconic acid, and fumaric acid. Examples of the saturated fatty acid having 8 or more carbon atoms include stearic acid, isononanoic acid, and dodecylbenzenesulfonic acid. There is, but is not limited to this.

The amount of the ethylenically unsaturated double bond compound which may be added and the saturated fatty acid having 8 or more carbon atoms may be 0.1 parts by weight to 5.0 parts by weight based on 100 parts by weight of the entire photocurable discoloration resin composition. If less than 0.1 part by weight, the color tone after curing appears light. If it exceeds 5.0 parts by weight, the color development is good, but the initial color before curing has a disadvantage of darkening.

The usage-amount of the (B) photocurable oligomer compound used for this invention uses 20-60 weight part when the sum total of (B) component and following (C) component is 100 weight part.

Hereinafter, the urethane-modified (meth) acrylate according to the present invention will be described in detail.

(b1) As the diol compound having a number average molecular weight of 200 or less [hereinafter, referred to as 'component (b1)'), a compound having a molecular weight of 200 or less among various saturated or unsaturated alkyl compounds on the market is used, and is represented by the following formula (1) The compound which has can be used.

[Formula 1]

HO- (R ₁ ) -OH

Where

R ₁ is a saturated or unsaturated group containing only 2 to 12 carbon atoms and a hydrogen atom.

Specific examples of the compound of Formula 1 include 1,9-nonanediol, octanediol, 2-methyl-1,8 octanediol, 2-butyl-2ethyl-1,3-propanediol, ethylene glycol, propylene glycol, butanediol , Hexanediol, heptanediol or decanediol may be used alone or in combination of two or more, but is not limited thereto.

When making 1 equivalent of diisocyanate groups, it can be used so that the hydroxyl group of a compound (b1) may be 0.5-0.8 equivalent ratio.

The number average molecular weight of the component (b1) affects the flexibility of the resulting cured product (film), the surface adhesion of the final film obtained, and the like, and when the molecular weight is 200 or more, the price is expensive or the film tends to be too flexible. It is preferable that the number average molecular weights of (b1) are 100-200.

(b2) As the diol compound having a number average molecular weight of 1,000 to 3,000 (hereinafter referred to as 'component (b2)'), there are commercially available polyolefin diol compounds, and specific examples thereof include polyethylene diol, polypropylene diol, and polyisoprene. Diol, hydrogenated butadiene diol, poly (ethylene-co-butylene) diol, polytetramethylene glycol or polybutenediol may be used alone or in combination of two or more, but is not limited thereto.

The number average molecular weight of the component (b2) affects the flexibility of the cured product (film) obtained with the component (b1), that is, the elongation of the cured product, and the number average molecular weight is preferably 1,000 to 3,000, preferably 2,000 to 3,000. Is good. When the molecular weight of the component is more than 3,000, not only the price is high, but also the viscosity is high, the workability is poor, and if it is 1,000 or less, there is a tendency that the surface adhesiveness of the final film and the stretching force are insufficient. Therefore, proper ratio adjustment of (b1) and (b2) components is very important for the expression of cost, workability and final physical properties. The number average molecular weight obtained by this invention was measured by the gel permeation chromatography method, and was quantified using the standard polystyrene calibration curve.

When the amount of the component (b2) is used as the equivalent of (b3) diisocyanate group, the hydroxyl group is used at a ratio of 0.1 to 0.5 equivalents.

(b3) As a diisocyanate compound which has two isocyanate groups in 1 molecule (henceforth "a component (b3)"), for example, toluene-2,4-diisocyanate, 1,6-hexamethylene diisocyanate, xylene Diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate and hydrogenated additives thereof and the like, but is not limited thereto. The said (b3) component is used individually or in combination of 2 or more types. The amount of the component (b3) is used so that the diisocyanate group equivalent of the component (b3) is 0.1 to 1.0 equivalents more than the total hydroxyl group equivalent of the compound used as the component (b1) and (b2).

(b4) As a photopolymerizable monofunctional diluent (hereinafter referred to as 'component (b4)'), a linear or cyclic compound having an ethylenically unsaturated double bond represented by the following general formula (2) without having a polar functional group such as a hydroxyl group, an amine group, or a carboxyl group An aliphatic (meth) acrylate compound is used alone or in combination of two or more thereof.

[Formula 2]

H ₂ C = CHR ₁ -COO-R ₂

In the above formula, R ₁ is hydrogen or CH ₃ and R ₂ is an alkyl structure having a linear or cyclic aliphatic structure consisting of only 1 to 12 carbon atoms and hydrogen.

Specific examples of the compound of Formula 2 include methyl (meth) acrylate, lauryl (meth) acrylate, isononyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ( Meta) acrylate or dicyclopentanyloxyethyl (meth) acrylate may be used alone or in combination of two or more, but is not limited thereto.

(b5) A hydroxyl group-containing (meth) acrylate monomer in a (meth) acrylate monomer having a number average molecular weight of 300 or less (hereinafter referred to as 'component (b5)') having one of a hydroxyl group, an amine group and a carboxyl group in one molecule Examples of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylic Examples of the amine group-containing (meth) acrylate monomer include, but are not limited to, diethylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, and the like, but are not limited thereto. Examples of the containing (meth) acrylate monomers include (meth) acrylic acid, 2-acryloyl oxy ethyl succinic acid, 2- (meth) acryloyl oxy ethyl succinic acid, 2-acryloyl oxy ethyl phthalic acid, 2- (meth ) By oxyethyl acid, 2-acryloyl acryloyloxyethyl hexahydrophthalic acid, 2- (meth) but include acryloyloxyethyl hexahydrophthalic acid, without being limited thereto. The hydroxyl group, amine group, and carboxyl group-containing (meth) acrylate monomer compound may be used alone or in combination of two or more thereof.

(b6) As an ethylenically unsaturated compound having two carboxyl groups in one molecule [hereinafter referred to as 'component (b6)'], for example, fumaric acid and itaconic acid may be used alone or in combination of two kinds, but are not limited thereto. It doesn't happen.

In the present invention, in the component (b), the amount of the compound having the components (b1) to (b3) is 0.5 to 0.8 equivalents of the hydroxyl group of the component (b1) relative to 1 equivalent of the isocyanate group of the component (b3) ( The hydroxyl groups of the component b2) are used in an amount of 0.1 to 0.5 equivalents, and the sum of the hydroxyl groups of the component (b1) and the component (b2) is 0.6 to 0.9 equivalents to 1 equivalent of the isocyanate group of the component (b3), thereby diisocyanate group It is made into the polymer obtained by making it react with 0.1 to 0.4 equivalent excess.

If the component (b1) is less than 0.5 equivalent to 1 equivalent of the isocyanate group of the component (b3), the possibility of surface tackiness increases. If the component is less than 0.8 equivalent, the flexibility of the cured product is low. Falls, the viscosity is too high if 0.5 equivalent or more, workability is likely to be poor.

In the present invention, the component (b1), (b2) and (b3) in the component (b) may be combined and reacted to obtain a urethane compound, and the urethane reaction may be carried out at 75 to 95 ° C. The reaction is completed within 1.5 hours. The urethane reaction of the present invention is reacted in the presence of (b4) a reactive diluent, and the content of the component (b4) is 20 to 60 parts by weight when the total amount of the components (b1) to (b3) is 100 parts by weight. The reaction is preferably 30 to 50 parts by weight. When the amount is less than the weight part, the viscosity after the urethane reaction is too high, and when it is 60 parts by weight or more, the molecular weight of the polymer grows too late, resulting in a long reaction time.

One or more of the above (b5) components and one or more of the above (b6) components are mixed and used, and the amount of each component used is 0.1 to 0.4 equivalents of the unreacted diisocyanate group of the (b3) component (b5). And the total amount of hydroxyl, amine or carboxyl equivalents of component (b6) are added in an amount of 0.1 to 0.5 equivalents and reacted.

Components (b5) and (b6) react the isocyanate group remaining after the completion of the urethane reaction with a (meth) acryl monomer having one of a hydroxy group, an amine group and a carboxyl group and a compound having an ethylenically unsaturated double bond (meth) acryl Compound (b5) is 0.45 to 1.3 equivalents and component (b6) is 0.05 to 0.2 equivalents based on 1 equivalent of isocyanate of the component (b3). The sum of (b6) should be 0.5 to 1.5 equivalents. If the sum of the components (b5) and (b6) is less than 0.5 equivalents, the hydrophilic isocyanate groups remain in the final cured product without being modified with (meth) acrylate, resulting in the possibility of surface tackiness and the increase in the water content, thereby reducing the moisture permeability. In addition, when 1.5 equivalent or more, the final cured product may have a content of a polar functional group such as a hydroxyl group, an amine group, and a carboxyl group in the polymer main chain, thereby increasing the water content.

(B5) and (b6) addition reaction of this invention is good to complete by reaction within 1.5 hours at 75-95 degreeC similarly to a urethane reaction.

The number average molecular weight of the (meth) acrylic-modified urethane compound prepared from component (B) according to the present invention is 5,000 to 40,000, and when the number average molecular weight is 5,000 or less, the adhesion to glass and polyimide is poor. There is a problem that the workability is lowered because the viscosity is too high.

The (meth) acrylic-modified urethane compound prepared from the component (A) is added in an amount of 20 to 60 parts by weight based on 100 parts by weight of the total of the (B) photo (ultraviolet) curable monomer compound described later. In the case of parts by weight or less, the properties such as surface hardenability, stretching force, strength, and the like tend to be generally lowered, and in the case of exceeding 60 parts by weight, the adhesive strength is lowered.

[Component (C)]

(C) photopolymerizable monomer component, (c1) monofunctional acrylate having a polar hydroxyl group, (c2) linear monofunctional acrylate having no polar functional group such as hydroxyl group, (c3) ethylenically unsaturated double bond and cyclic aliphatic It is used combining 1 type (s) or 2 or more types from the compound which consists of a photopolymerizable monomer which has group, (c4) polyfunctional acrylate which has 2-5 acryl functional groups, etc.

(C) Monofunctional acrylate monomer which has a hydroxyl group of (c1) polarity as a monomer component which can be photopolymerized (henceforth "component (c1)"), for example, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, and the like, which may be used alone or in combination of two or more, but is not limited thereto.

(c2) As a monofunctional acrylate monomer which does not have a polar group (henceforth "a component (c2)"), methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acryl Latex, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isononyl acrylate, tridecyl (meth) acrylate, and the like. Of these, it may be used alone or in combination of two or more, but is not limited thereto.

(c3) As a photopolymerization monomer (henceforth "component (c3)") which has an ethylenically unsaturated double bond and a cyclic aliphatic group, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobonyl (Meth) acrylate, norobornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxy One having a vinyl group, such as ethyl (meth) acryl vinyl norbornylone, vinyl norbornanane, or the like may be used, but it may be used alone or in combination of two or more, but is not limited thereto.

(c4) Examples of the polyfunctional acrylate monomer having two to five acrylic functional groups (hereinafter referred to as '(c4) component') include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and 1,6-hexane In diol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate alone Or it may be used in combination of two or more, but is not limited thereto.

The component (C) is blended in an amount of 40 to 80 parts by weight, preferably 50 to 70 parts by weight based on 100 parts by weight in total with the component (B). In the present invention, the effect of the content of the component (C) on the color is that when the irreversible dye is used, the color change may have some slight differences depending on the components, but there is no problem to return after discoloration. The higher the content of the component (c1) is, the more likely the final color is expressed. In addition, when the blending amount of component (C) is less than 40 parts by weight, the adhesive strength with the polyimide is not sufficient. When the content of the component (C) exceeds 80 parts by weight, the transparency of the resulting coating film is increased, and the adhesion with the glass substrate is lowered. The concentration of the resin composition tends to be low, and the properties such as surface hardenability, elongation, strength, and the like tend to decrease overall.

(C) The photopolymerizable monomer is 0.1-5 parts by weight of a monofunctional acrylate having a hydroxyl group of (c1) polarity and (c2) a straight chain having no polar functional group, based on 100 parts by weight in total with (B) component. 1 to 10 parts by weight of monofunctional acrylate having a structure, (c3) 20 to 60 parts by weight of a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group, and (c4) a polyfunctional acrylate having 2 to 5 acrylic functional groups. It may include 2 to 15 parts by weight.

[Component (D)]

(D) As a photoinitiator (henceforth "(D) component"), a carbonyl type photoinitiator, a sulfide type photoinitiator, a quinone type photoinitiator, an azo type photoinitiator, a peroxide type photoinitiator, etc. are mentioned, for example. Specifically, benzophenone, benzyl, benzoin, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethyl Aminopropiophenone, p, p'-bisdiethylaminobenzophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy- 2-methyl-1-phenyl-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-diethoxyacetophenone, 4-N , N'-dimethylacetophenone,, benzoquinone, anthraquinone and the like, diphenyldizulide, dibenzyldisulfide, tetraethylthiuram disulfide, tetramethylammonium Ummonosulfone, azobisisobutyronitrile, 2,2'-azobispropane, hydrazine, thioxanthone, 2-methyl thioxanthone benzoyl peroxide, di-t-butylperoxide, 2,4,6-trimethyl Benzoyl-diphenyl-phosphineoxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-hydroxy-1-4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl-2-methyl-propane-1-one and the like, and any one of them, preferably at least two or more, particularly preferably at least three Use in combination above.

The photopolymerization initiator can be selected according to the use by dividing it into surface curing and deep curing depending on the thickness of the coating film.In consideration of the thickness of the cured product, the intensity of the light source and the exposure time, one or more of two or more kinds should be used. The coating film which hardens the surface and core part of hardened | cured material can be obtained. It is preferable to use at least 3 types or more from the point which can obtain the coating film in which the surface and core part of a final hardened | cured material are uniformly hardened | cured.

In the present invention, the component (D) is 1 to 10 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the total of (B) and (C) component. When the amount of use is less than 1 part by weight, it is difficult to obtain a desired curing rate, and when it is 10 parts by weight or more, the molecular weight of the resin after curing may become small, resulting in surface adhesiveness. However, it is selected in consideration of the overall situation such as the curing time, light source, the thickness of the coating film.

[Component (E)]

(E) As the additive component (hereinafter, referred to as '(E) component'), a silane coupling agent, a thermal polymerization inhibitor, or a saturated fatty acid having 8 or more carbon atoms may be further used. For example, vinyl trimethoxy silane, vinyl triethoxy silane, trimethoxy silanyl (meth) acrylate, vinyl triethoxy silanyl (meth) acrylate, etc. can be used individually or in combination of 2 or more types. If necessary, a thermal polymerization inhibitor may be included, and specific examples thereof may be selected from hydroquinone, methyl ether hydroquinone, 2,6-di-tertiarybutyl-4-methyl phenol, and the like. Photochromic dyes develop chromogenic properties and retain at least 8 carbon-saturated fatty acids that are not covalently bonded to the resin, but can be bonded in the form of hydrogen bonds, such as stearic acid, decanoic acid and isononanoic acid. A small amount of dodecylbenzenesulfonic acid or the like may be added alone or in combination of two or more, but is not limited to the above-mentioned components.

In the present invention, the component (E) may be used by adding 0.1 to 7.0 parts by weight based on 100 parts by weight of the total of the components (B) and (C).

[Photocurable moisture proof insulation coating for printed circuit boards]

The above-mentioned photocurable discoloration resin composition can be used for the photocurable moisture proof insulating paint for printed circuit boards. In this case, a filler, a modifier, an antifoamer, etc. can be used for the photocurable resin composition of this invention as needed. It is possible to add and use arbitrarily.

As a filler, commercially available fillers such as magnesium oxide, aluminum hydroxide, calcium carbonate and the like are used, and 0.1 to 100 parts by weight is added to 100 parts by weight of a moisture proof insulating material.

Modifiers include, for example, leveling agents to improve leveling properties, and specific examples are selected from polyether modified dimethyl polysiloxane copolymers, polyester modified dimethyl polysiloxane copolymers, and polyether modified dimethyl alkyl polysiloxane copolymers. 0.01 to 10 parts by weight based on 100 parts by weight of moisture proof insulating material is used.

As the antifoaming agent, for example, known antifoaming agents such as silicone oil, fluorine oil, and polycarboxylic acid polymer are used. Usually, 0.01 to 50 parts by weight is added to 100 parts by weight of the moisture proof insulating material.

[Electronic parts]

In the present invention, the electronic component is an electronic component manufactured using the photocurable moisture proof insulating coating agent described above, and the electronic component is a microcomputer, a transistor, a capacitor, a resistor, a transformer, a printed circuit board having the same, and the like. Lead wires, film substrates and the like bonded to such electronic components are also included. Moreover, the signal input part of flat panel display panels, such as a liquid crystal display panel, a plasma display panel, and an organic light emitting diode panel, also corresponds to an electronic component.

[Manufacturing Method of Electronic Components]

In the present invention, the electronic component is produced by insulating the electronic component using a photocurable moisture proof insulating coating agent. As a manufacturing method of an electronic component, after applying the above-mentioned moisture-proof insulating paint to the electronic component according to a generally known deposition method, spray method, nozzle spray method, etc., the high-pressure mercury lamp, metal halide lamp, LED, etc. Is irradiated with ultraviolet rays to cure the coating film of the moisture-proof insulating coating applied to the electronic component to obtain the electronic component.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples described below.

Synthesis Example 1

[Urethane Manufacturing Steps]

10 parts by weight of 2-butyl-2-ethyl-1,3-propanediol and a poly (ethylene-co-butylene) diol in a clean 4L glass reactor equipped with a stirrer, a thermometer and a cooling jacket. , GI-2000, Molecular weight about 2,500)] 65 parts by weight, 45 parts by weight of isobornyl acrylate and 25 parts by weight of isophorone diisocyanate as a diluent, and stirred well, after raising the reactor temperature to 85 ℃, dibutyl tin 0.02 parts by weight of dilaurate was added and reacted for 1 hour 30 minutes.

[(Meth) acrylic modified urethane manufacturing step]

10 parts by weight of 2-hydroxyethyl (meth) acrylate and 0.2 parts by weight of itaconic acid were added thereto while maintaining the temperature at 85 ° C, and the reaction was further performed for 1 hour. The reaction was measured by IR to confirm that the isocyanate group disappeared, and then the reaction was terminated to obtain a urethane compound having an ethylenically unsaturated double bond (hereinafter referred to as (H-0)).

Synthesis Example 2

[Urethane Manufacturing Steps]

10 parts by weight of 2-butyl-2-ethyl-1,3-propanediol and a poly (ethylene-co-butylene) diol in a clean 4L glass reactor equipped with a stirrer, a thermometer and a cooling jacket. , GI-2000, Molecular weight about 2,500)] 35 parts by weight, 45 parts by weight of isobornyl acrylate and 65 parts by weight of isophorone diisocyanate as a reactive diluent are stirred well and the reactor temperature is raised to 85 ℃, dibutyl 0.02 parts by weight of tin dilaurate was added and reacted for 1 hour 30 minutes.

[(Meth) acrylic modified urethane manufacture]

10 parts by weight of 2-hydroxyethyl (meth) acrylate was added thereto while maintaining the temperature at 85 ° C, and the reaction was further performed for 1 hour. The reaction was measured by IR to confirm that the isocyanate group disappeared, and then the reaction was terminated to obtain a urethane compound having an ethylenically unsaturated double bond (hereinafter referred to as (U-0)).

Synthesis Example 3

[Product of carbonate group introduction urethane]

10 parts by weight of 1,9-nonanediol in a clean 4L glass reactor equipped with a stirrer, a thermometer and a cooling jacket, polycarbonate diol (manufactured by Kuraray Co., Ltd., product name: PNOC-2000, number average molecular weight: about 2000) 30 By weight, 60 parts by weight of isophorone diisocyanate and 40 parts by weight of isobornyl acrylate as a reactive diluent were stirred well and the reactor temperature was raised to 80 ° C., and 0.1 parts by weight of dibutyltin dilaurate was added for reaction for 3 hours. I was.

[Production of carbonate group (meth) acryl modified urethane]

20 parts by weight of 2-hydroxyethyl (meth) acrylate was further added thereto while maintaining the temperature at 80 ° C, and the reaction was carried out for 1 hour. The reaction was measured by IR to confirm that the isocyanate group disappeared, and then the reaction was terminated to obtain a urethane compound having an ethylenically unsaturated double bond (hereinafter referred to as (C-0)).

Example 1

50 parts by weight of the (meth) acryl-modified urethane resin (H-0) obtained in Synthesis Example 1, 5 parts by weight of 2-hydroxyethyl (meth) acrylate, 3 parts by weight of lauryl acrylate, and 32 parts by weight of isobornyl acrylate. 5 parts by weight of pentaerythritol tetraacrylate, 5 parts by weight of vinyltrimethoxy silane, 1.5 parts by weight of benzophenone, 2-methyl-1- (4-methylthio) phenyl-2-morpholino-propane-1- ON 5 parts by weight, 1.5 parts by weight of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 0.5 parts by weight of 4,4 ', 4 "-methylidinetris (N, N-dimethylaniline) at 60 ° C 1 The mixture was mixed well for a time to obtain a photo (ultraviolet) curable resin composition (H-1).

[Example 2]

Except that 40 parts by weight of (meth) acrylic modified urethane resin (H-0) and 42 parts by weight of isobornyl acrylate were used in the same formulation and manner as in Example 1, except that the optical (ultraviolet) curable resin composition was used. (H-2) was obtained.

Example 3

Except for using the (meth) acrylic modified urethane resin (H-0) in Example 1 and 35 parts by weight of isobonyl acrylate in the same formulation and manner as in Example 1, the photo (ultraviolet) curable resin composition (H-3) was obtained.

Example 4

Except for using 3 parts by weight of isononyl acrylate instead of lauryl acrylate in Example 3 to obtain a photo (ultraviolet) curable resin composition (H-4) in the same formulation and manner as in Example 3.

Example 5

Except for using 2.9 parts by weight of isononyl acrylate and 0.1 part by weight of isononyl acrylic acid in Example 4, a photo (ultraviolet) curable resin composition (H-5) was obtained in the same formulation and manner as in Example 4.

Comparative Example 1

A photo (ultraviolet) curable resin composition in the same formulation and manner as in Example 1, except that the photochromic dye 4,4 ', 4 "-methylidritris (N, N-dimethylaniline) was not used in Example 1 (H-6) was obtained.

 Comparative Example 2

15 parts by weight of the (meth) acrylic-modified urethane resin (H-0) obtained in Synthesis Example 1, 5 parts by weight of lauryl acrylate, 80 parts by weight of isobornyl acrylate, and 4 parts by weight of benzophenone at 60 ° C. for 1 hour. It mixed and obtained the photo (ultraviolet) curable resin composition (H-7).

Comparative Example 3

Except that 70 parts by weight of (meth) acrylic-modified urethane resin (H-0) and 25 parts by weight of isobornyl acrylate were used in Comparative Example 2, the optical (ultraviolet) curable resin composition was prepared in the same formulation and manner as in Comparative Example 2. H-8).

[Comparative Example 4]

A commercially available acrylic base product "CPF-FS4" (H-9), which is a commercially available ultraviolet curing adhesive for protecting PDP electrodes, was used.

[Comparative Example 5]

Shin-Etsu Silicone Base "SEALANT-OK" (H-10), a silicone moisture-curable protective agent, was used.

The mixing | blending characteristic of Example 1-the comparative example 5 is shown in Table 1.

Physical properties of the photocurable compositions (H-1) to (H-8) obtained by the above method were measured by the following methods. It is an object of the present invention to provide ease of quality control through color comparison before and after curing, while having excellent adhesion to glass and polyimide, good moisture resistance and insulation, and thus, adhesion to glass plates, moisture permeability, water absorption, surface and In addition to volume resistivity, color change before and after curing was evaluated.

① adhesion

The photocurable compositions (H-1) to (H-8) obtained in the above examples and comparative examples were coated on a glass plate (20mm × 100mm × 2mm) with a thickness of 1mm and 10mm × 100mm in width and length to mount a metal halide lamp. Using a UV irradiation device (Uniram, metal halide lamp light source: 500W) was cured to the time of complete curing for each sample at an irradiation distance of 20cm to prepare a specimen bonded to the glass plate. Specimens adhered to the glass plate were measured by a 180 ° peel test method at 100 mm / min using a universal tensile tester (manufactured by Hounsfield).

② moisture permeability

After the moisture permeability measurement specimens were prepared to have a thickness of 0.3 mm with the photocurable compositions (H-1) to (H-8) obtained in the above Examples and Comparative Examples, and stored at constant temperature and humidity under the conditions of 38 ± 2 ° C. and 100% RH. The moisture vapor permeability for 24 hours was measured. (Water vapor permeability tester: PERMATRAN-W, Model 3/61 (MOCON, USA), Test method: KS M 3088: 2004)

③ absorption

After curing the photocurable compositions (H-1) ~ (H-8) obtained in the above Examples and Comparative Examples to a thickness of 1mm, prepared 10 pieces for each sample to a size of 10mm × 10mm to measure the initial weight Then, after leaving for 2 hours in 100 ℃ boiling water was measured the weight change was expressed as a percentage of the weight change.

④ Curing time

The resin composition of Examples 1 to 5 and Comparative Examples 1 to 5 was injected into a cell of 10 mm x 10 mm x 3 mm, and the light intensity was 500 mW / cm ² using an ultraviolet irradiation device (manufactured by Uniram) equipped with a metal halide lamp. The curing time was measured in seconds with the strength of.

⑤ Color change

The resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were completely cured to a size of 1 mm × 10 mm × 10 mm, and color values were measured by measuring color concentration using a colorimeter (500 series, manufactured by X-rite). The difference was over 0.3 and the color was displayed when color could be distinguished visually.

The measured results are shown in Table 1.

Raw material name Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 H-1 H-2 H-3 H-4 H-5 H-6 H-7 H-8 H-9 H-10 H-0 50 40 35 35 35 50 15 70 2-hydroxyethyl (meth) acrylate 5 5 5 5 5 5 - - Lauryl acrylate 3 3 3 - - 3 5 5 Isononyl acrylate - - - 3 2.9 3 - - Isononyl acrylic acid - - - - 0.1 - - - Isobonylacrylate 32 42 47 47 47 32 80 25 Pentaerythritol tetraacrylate 5 5 5 5 5 5 - - Vinyltrimethoxysilane 5 5 5 5 5 5 - - Benzophenone 1.5 1.5 1.5 1.5 1.5 1.5 4 4 2-methyl-1- (4-methylthio) phenyl-2-morpholino-propan-1-one 5 5 5 5 5 5 - - 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 1.5 1.5 1.5 1.5 1.5 1.5 - - 4.4 ', 4 "-methylidritris (N, N-dimethylaniline) 0.5 0.5 0.5 0.5 0.5 - - - Item unit Curing time sec 6 6 6 6 6 6 9 8 19 550 Adhesion N / m 310 280 270 270 260 305 150 190 290 180 Moisture permeability g / m224h 13 13 14 12 13 13 16 17 35 41 Absorption rate % 0.01 0.03 0.02 0.02 0.13 0.01 1.23 1.05 2.5 5.5 Color change Before hardening - Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency After curing - blue blue blue blue blue Transparency Transparency Transparency Transparency Transparency

As shown in Table 1, in the case of blending the Example, the curing time of the silicone moisture curable type of Comparative Example 5 or the acrylic base of Comparative Example 4 is very fast compared to the protective agent, and high productivity can be obtained. Very good results were obtained. In addition, it can be seen that the moisture permeability and insulation properties are very good. In particular, in the case of Example 1 and Comparative Example 1, the physical properties such as adhesive strength are similar when the photochromic dye is included and when the same formulation is not included, but the color change before and after curing is obvious, so that the degree of curing can be determined only by the color change. Therefore, it is possible to quickly and easily grasp the quality defects due to the failure of the equipment such as the curing device, can provide breakthrough convenience in quality control. Unlike conventional photocurable resins having the characteristics of similar color realization before and after curing (colorless or the same color appearance before and after curing even when colorant is added if necessary), the present invention clearly shows the color change before and after curing. Differentiated and made a breakthrough in quality control.

Example 6

50 parts by weight of the (meth) acryl-modified urethane resin (U-0) obtained in Synthesis Example 2, 5 parts by weight of 2-hydroxyethyl (meth) acrylate, 3 parts by weight of lauryl acrylate, 37 parts by weight of isobornyl acrylate 5 parts by weight of pentaerythritol tetraacrylate, 5 parts by weight of vinyltrimethoxy silane, 3 parts by weight of benzophenone, 0.5 parts by weight of 4,4 ', 4 "-methylidinetris (N, N-dimethylaniline) 60 The mixture was mixed well at 1 ° C. for 1 hour to obtain a photo (ultraviolet) curable resin composition (A-1).

Example 7

0.5 parts by weight of 4,4 ', 4 "-methylidinetris (N, N-dimethylaniline) to 100 parts by weight of commercially available (meth) acrylic-modified urethane resin TF-3348-200, Japan TF-3348-200, for 1 hour at 60 ° C The mixture was mixed well to obtain a light (ultraviolet) curable resin composition (A-2).

Example 8

Photocurability in the same formulation and manner as in Example 6, except that 50 parts by weight of the carbonate group-introduced (meth) acrylic-modified urethane resin (C-0) obtained in Synthesis Example 3 was used instead of Synthesis Example 2 in Example 6. Resin composition (A-3) was obtained.

Example 9

To 0.5 parts by weight of 4,4 ', 4 "-methylidinetris (N, N-dimethylaniline) at 100 parts by weight of A350K1, a Japanese (meth) acryl-modified urethane resin, manufactured by Kyoritsu Co., Ltd. The photo (ultraviolet) curable resin composition (A-4) was obtained.

Example 10

50 parts by weight of the (meth) acryl-modified urethane resin (U-0) obtained in Synthesis Example 2, 5 parts by weight of 2-hydroxyethyl (meth) acrylate, 3 parts by weight of lauryl acrylate, 37 parts by weight of isobornyl acrylate Parts, 5 parts by weight of pentaerythritol tetraacrylate, 5 parts by weight of vinyltrimethoxy silane, 3 parts by weight of benzophenone, 0.5 part by weight of spiroxazine dye (UK, James Robinson, trade name; Oxford Blue) at 60 ° C. The mixture was mixed well for 1 hour to obtain a photo (ultraviolet) curable resin composition (A-5).

[Comparative Example 6]

The photocurable resin composition (A-) was prepared in the same formulation and manner as in Example 6, except that the photochromic dye 4,4 ', 4''-methylidritris (N, N-dimethylaniline) was not used in Example 6. 6) was obtained.

Comparative Example 7

The photocurable resin composition (A-) was prepared in the same formulation and manner as in Example 7, except that the photochromic dye 4,4 ', 4''-methylidritris (N, N-dimethylaniline) was not used in Example 7. 7) was obtained.

Comparative Example 8

The photocurable resin composition (A-) was prepared in the same formulation and manner as in Example 8, except that the photochromic dye 4,4 ', 4''-methylidritris (N, N-dimethylaniline) was not used in Example 8. 8) was obtained.

[Comparative Example 9]

The photocurable resin composition (A-) was prepared in the same formulation and manner as in Example 9, except that the photochromic dye 4,4 ', 4''-methylidritris (N, N-dimethylaniline) was not used in Example 9. 9) was obtained.

The blending characteristics of Examples 6 to 10 and Comparative Examples 6 to 9 are shown in Table 1.

Physical properties of the photocurable compositions (A-1) to (A-8) obtained by the above method were measured by the above-described method. The purpose of the present invention is to provide the convenience of quality control through color comparison before and after curing while maintaining the adhesive strength and moisture-proof insulation properties, which are inherent characteristics of conventional commercial photocurable resin composition, adhesion strength and moisture permeability In addition to the water absorption, the color change before and after curing was evaluated.

The measured results are shown in Table 2.

Raw material name Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 U-0 50 50 50 C-0 50 50 Hitachi Temple (Sun) Tuffy 3348-200 100 100 Kyoritsu Corporation (Sun) A350K1 100 100 2-hydroxyethyl (meth) acrylate 5 5 5 5 5 Lauryl acrylate 3 3 3 3 3 Isobonylacrylate 37 37 37 37 37 Pentaerythritol tetraacrylate 5 5 5 5 5 Vinyltrimethoxysilane 5 5 5 5 5  Benzophenone 3 3 3 3 3 4.4 ', 4 "-methylidritris (N, N-dimethylaniline) 0.5 0.5 0.5 0.5 - - - - Spirooxide dyes 0.5 Item unit Curing time sec 15 6 15 16 15 15 6 15 16 Adhesion N / m 310 310 300 270 305 310 310 300 270 Moisture permeability g / m224h 13 13 14 18 13 13 13 14 18 Absorption rate % 0.01 0.03 0.94 1.04 0.01 0.13 0.02 0.95 1.05 Color change Before hardening - Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency After curing - Dark blue Light blue Dark blue Light blue Light blue Transparency Transparency Transparency Transparency

As shown in Table 2, when the photochromic dye is added as in the case of blending Examples 6 to 10, the initial color is transparent to the photocurable after the photocuring, unlike the compound composition in which the photochromic dye of Comparative Examples 6 to 9 is not added. It can be seen that light blue or dark blue expresses a distinct color. On the other hand, in the case of the same compounding composition as shown in Example 6 and Comparative Example 6, Example 7 and Comparative Example 7, Example 8 and Comparative Example 8, Example 9 and Comparative Example 9, the existing physical properties such as adhesion, moisture content, etc. without significant change It can be seen that the color expression. Such characteristics can provide a convenient convenience in quality control because it can quickly and easily identify the quality defects due to the failure of the equipment, such as a curing device when manufacturing electronic components. Unlike conventional photocurable resins having the characteristics of similar color realization before and after curing (colorless or the same color appearance before and after curing even when colorant is added as needed), the present invention clearly shows the color change before and after curing. Differentiated and made a breakthrough in quality control.

Claims (25)

A photocurable discoloration resin composition comprising a photocurable compound and a photochromic dye, wherein the color is changed before and after photocuring. The photochromic dye according to claim 1, wherein the photochromic dye is 4,4 ', 4 "-methylidritris (N, N-dimethylaniline), a spiroxazine photochromic dye, a naphthopyranic photochromic dye, and derivatives thereof. At least one selected from the group consisting of. The photocurable compound according to claim 1 or 2, wherein the photocurable compound is selected from the group consisting of urethane-modified (meth) acrylates, carbonate-introduced urethane-modified (meth) acrylates and silicone-introduced urethane-modified (meth) acrylates. Composition. The composition of claim 1 or 2, wherein the composition further comprises a photopolymerizable monomer and a photopolymerization initiator. 5. The photopolymerizable monomer according to claim 4, wherein the photopolymerizable monomer comprises a monofunctional acrylate having a polar hydroxyl group, a linear monofunctional acrylate having no polar functional group, a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group, and an acrylic functional group. At least one member selected from the group consisting of 2 to 5 polyfunctional acrylates. The composition according to claim 4, wherein the photopolymerization initiator is selected from the group consisting of a carbonyl photopolymerization initiator, a sulfide photopolymerization initiator, a quinone photopolymerization initiator, an azo photopolymerization initiator, and a peroxide photopolymerization initiator. The composition according to claim 4, wherein the composition further comprises an ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms. The total amount of the photocurable compound and the photopolymerizable monomer is 100 parts by weight, the photochromic dye is 0.1 to 10 parts by weight, the photocurable compound is 20 to 60 parts by weight, and the photopolymerizable monomer is 40 to 80 parts by weight, and the photopolymerization initiator is 1 to 10 parts by weight. The composition according to claim 7, wherein the ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group is selected from at least one member selected from the group consisting of acrylic acid, (meth) acrylic acid, itaconic acid and fumaric acid. 8. The composition of claim 7, wherein the saturated fatty acid having at least 8 carbon atoms is selected from the group consisting of stearic acid, isononanoic acid and dodecyl benzenesulfonic acid. The composition according to claim 7, wherein the amount of the ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms is 0.1 parts by weight to 5.0 parts by weight based on 100 parts by weight of the photocurable discoloration resin composition. The amount of the ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms is 0.1 parts by weight to 100 parts by weight based on the total weight of the photocurable compound, the photopolymerizable monomer and the photopolymerization initiator. 5.0 parts by weight of the composition. The method according to claim 1 or 2, wherein the photocurable compound,
Preparing a urethane compound by reacting a diol compound having a molecular weight of 200 or less and a diol compound having a molecular weight of 1,000 to 3,000 with a diisocyanate compound having two isocyanate groups in one molecule together with a diluent including a urethane ethylenically unsaturated double bond; And
The urethane compound prepared above is a urethane-modified (meth) acrylate prepared by reacting a compound having one group selected from a hydroxyl group, an amine group or a carboxyl group in one molecule with an ethylenically unsaturated compound having two carboxyl groups. , Composition. A method of irreversibly changing the color before and after photocuring by adding a photochromic dye to the photocurable compound. The method of claim 14, wherein the quality of the product comprising the photocurable compound is measured by the color change. The photochromic dye according to claim 14 or 15, wherein the photochromic dye is 4,4 ', 4 "-methylidritris (N, N-dimethylaniline), a spiroxazine photochromic dye, a naphthopyranic photochromic dye and At least one selected from the group consisting of derivatives thereof. The method according to claim 14 or 15, wherein the photocurable compound is selected from the group consisting of urethane-modified (meth) acrylates, carbonate-introduced urethane-modified (meth) acrylates and silicone-introduced urethane-modified (meth) acrylates. How. The method according to claim 14 or 15, wherein the photochromic dye is an irreversible photochromic dye or using a reversible photochromic fuel in irreversible conditions. The method of claim 18, wherein the irreversible conditions are conditions in which an ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms is further added. The method according to claim 19, wherein the ethylenically unsaturated double bond compound having a hydroxyl group or a carboxyl group is selected from at least one member selected from the group consisting of acrylic acid, (meth) acrylic acid, itaconic acid and fumaric acid. 20. The method of claim 19, wherein the saturated fatty acid having at least 8 carbon atoms is selected from the group consisting of stearic acid, isononanoic acid and dodecyl benzenesulfonic acid. Preparing a urethane compound by reacting a diol compound having a molecular weight of 200 or less and a diol compound having a molecular weight of 1,000 to 3,000 with a diisocyanate compound having two isocyanate groups in one molecule together with a diluent including a urethane ethylenically unsaturated double bond; And
A urethane-modified (meth) acrylate prepared by reacting the urethane compound prepared above with a compound having one group selected from one hydroxyl group, an amine group or a carboxyl group and an ethylenically unsaturated compound having two carboxyl groups. The photocurable discoloration coating agent for printed circuit boards containing the photocurable discoloration resin composition of Claim 1 or 2. An electronic component insulated with a photocurable discoloration coating agent for a printed circuit board according to claim 23. A method of using a reversible photochromic dye as an irreversible photochromic dye by using an ethylenically unsaturated double competitive compound having a hydroxyl group or a carboxyl group or a saturated fatty acid having 8 or more carbon atoms.