CN102559121A - Ultraviolet (UV)/moisture dual-cured laminated adhesive and preparation method thereof - Google Patents

Abstract

The invention discloses an ultraviolet (UV)/moisture dual-cured laminated adhesive and a preparation method thereof. The UV/moisture dual-cured laminated adhesive is prepared by mixing ultraviolet-curable (methyl) acrylate resin, moisture-curable modified (methyl) acrylate resin, a (methyl) acrylic reactive diluent, a moisture-curable (methyl) acrylic reactive diluent, a photoinitiator and a catalyst in an appropriate formula ratio. Compared with a moisture-cured laminated adhesive, the invention has the advantages that: the UV/moisture dual-cured laminated adhesive is quickly cured, the efficiency is high, and the production cost is reduced. Compared with a UV-cured laminated adhesive, the UV/moisture dual-cured laminated adhesive has the advantages that: the disadvantage that a shaded part cannot be cured is overcome; and the protection effect of glue is improved. According to the results, the adhesive fully meets the production process requirements of laminated adhesives which are applied to the protection of printed circuit boards (PCB) and laminated adhesives for the protection of chip on glass (COG).

Description

A kind of UV/ moisture dual cure laminated adhesive and preparation method thereof

Technical field

The present invention relates to polymeric material field, be specifically related to UV/ moisture dual cure laminated adhesive and preparation method thereof.

Background technology

Radiation curing refers to that UV-light (UV) and electron beam (EB) solidify, and is a kind of advanced person's surface treatment technology of material.It is to utilize UV/EB to cause to have chemically active liquid material rapid polymerization crosslinked, the instantaneous solidification film forming.Photocuring technology has fast setting, less energy-consumption, high-level efficiency, advantage such as pollution-free; Meet " 5E " principle fully: Efficient is efficient; The Enabling wide adaptability, Economical is economical, and Energy Saving is energy-conservation; Environmental Friendly environmental friendliness is a kind of eco-friendly green technology;

In recent years, the enhancing of Along with people's Environmental awareness and development of high-tech, the UV curing technology receives people and extensively payes attention to.What at present, domestic research was more is the application of UV curing technology aspect coating.As one of Application Areas of UV curing technology, the UV cured adhesive has obtained to develop rapidly abroad, and China compares with the area with developed country the research of UV cured adhesive, remains in bigger gap.The UV cured adhesive can replace traditional tackiness agent at special dimension, compares with traditional tackiness agent, and the UV cured adhesive has length storage period, do not contain advantages such as solvent, smell is low, curing speed is fast, bonding strength is high, production energy consumption is low.Therefore, the UV cured adhesive has a wide range of applications in fields such as optics, electronics, accurate apparatuses;

Along with the attention of household electric appliances to product reliability, this notion of general character overlay film is mentioned by increasing production firm, and major cause is that the general character overlay film can provide functions such as moistureproof, anti-salt fog, anti-electrostatic to product.Except that being used for electronic industry, the general character laminated adhesive just begins one's study domestic then rarely seen report abroad also having wide practical use aspect automotive industry, space flight and aviation industry, national defense industry and the biotechnology from the seventies in last century.UV-light (UV) solidifies the general character laminated adhesive because of extremely people's concern of energy-conservation and environment-friendly advantage that it had;

Because the solidification process of photocuring system by light-initiated, has certain restriction for shape, thickness, the color of solidifying object, can't realize photocuring like the zonule dash area.UV/ moisture dual cure laminated adhesive utilizes UV light fast setting, and the Special Areas in that UV-light is difficult to shine makes its crosslinking curing through moisture, thereby implements the provide protection to various complicated type wiring boards.

Summary of the invention

The objective of the invention is to overcome existing UV overlay film glue can not provide the effective protection, glue can't UV solidified shortcoming at dash area on the complicated type wiring board; A kind of UV/ moisture dual cure overlay film glue is provided, has the UV/ moisture dual cure laminated adhesive that UV fast setting, dash area are moisture cured, can satisfy complicated type wiring board special protection requirement.

Another object of the present invention provides a kind of preparation method of above-mentioned UV/ moisture dual cure laminated adhesive.

In order to realize the object of the invention, a kind of UV/ moisture dual cure laminated adhesive is proposed, said laminated adhesive is formed as follows by weight:

Acrylate resin 0～50

Moisture cured modified acrylic ester resin 0～50

Vinylformic acid reactive thinner 10～40

Moisture cured modified acroleic acid reactive thinner 10～40

Light trigger 0～10

Catalyzer 0～2

Said acrylate resin is one or more the mixture in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate and the modifier thereof;

Said moisture cured modification (methyl) acrylate resin general formula is following:

Wherein: m, n are respectively 1～4 integer, and R1 is acrylate group or methacrylate based group, and R2 is the moisture cured group that comprises NCO group or siloxane groups;

Said vinylformic acid reactive thinner is one or more the mixture in triglycerin diacrylate, triglycerin dimethyl propylene acid esters, ethoxyquin triglycerin diacrylate, THF propenoate, 1,6 hexanediol diacrylate, the third oxidation USP Kosher triacrylate, IBOA, isobornyl methacrylate, the 2-phenoxyethyl acrylate;

Said moisture cured modified acroleic acid reactive thinner general formula is following:

Wherein: a, b are respectively 1～3 integer, and R3 is acrylate group or methacrylate based group, and R4 is the moisture cured group that comprises NCO group or siloxane groups.

Said acrylate resin comprises the methacrylate resin that it is corresponding; Said moisture cured modified acrylic ester resin comprises the moisture cured modified methyl acrylic resin that it is corresponding; Said moisture cured modified acroleic acid reactive thinner comprises the moisture cured modified methacrylic acid reactive thinner that it is corresponding, and said epoxy acrylate comprises that its corresponding epoxy methacrylates, said urethane acrylate comprise that its corresponding urethane methacrylate, said polyester acrylate comprise that its corresponding polyester methacrylate, said polyether acrylate comprise polyethers methacrylic ester and modifier thereof that it is corresponding.

Said laminated adhesive also comprises other additives of 0～2 part, and said other additives are one or more the mixture in pigment, skimmer, flow agent, wetting agent, the dispersion agent.

Said light trigger is 2-hydroxyl-aminomethyl phenyl propane-1-ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, benzoin dimethylether, UVNUL MS-40, contraposition N, the different monooctyl ester of N-dimethylaminobenzoic acid, 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, 2; 4, the mixture of one or more in the 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester;

Said catalyzer is one or more the mixture in positive isopropyl titanate, tetrabutyl titanate, ethylacetoacetate titanium mixture, metatitanic acid four tert-butyl ester mixtures, two LAURIC ACID 99 MIN tin methides, the methyl aceto acetate tin composite.

The present invention also proposes a kind of method for preparing described UV/ moisture dual cure laminated adhesive, and said method is made up of following steps successively:

(a) acrylate resin, moisture cured modified acrylic ester resin, vinylformic acid reactive thinner, moisture cured modified acroleic acid reactive thinner mixed 10～60 minutes under high temperature, lucifuge, vacuum condition;

(b) adding light trigger mixed 10～60 minutes under room temperature, lucifuge, vacuum condition;

(c) add catalyzer, other additives, under room temperature, lucifuge, vacuum condition 10～60 minutes, it is uniformly dispersed.

Wherein, Said acrylate resin comprises that its corresponding methacrylate resin, said moisture cured modified acrylic ester resin comprise the moisture cured modified methyl acrylic resin that it is corresponding, and said vinylformic acid reactive thinner comprises that its corresponding methylacrylic acid reactive thinner, said moisture cured modified acroleic acid reactive thinner comprise the moisture cured modified methacrylic acid reactive thinner that it is corresponding.

The present patent application and the beneficial effect of compared with techniques in the past:

1, compares with the moisture-curable laminated adhesive, have fast setting, high-level efficiency, the characteristics that reduce production costs.

2, compare with UV solidified laminated adhesive, avoid the dash area can't the solidified defective, improve the provide protection of glue.

According to The above results, this tackiness agent satisfies laminated adhesive and COG (chip on glass) the chip protection manufacturing technique requirent that is applied to the pcb board protection fully.

Embodiment

For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, to further explain of the present invention;

The present invention selects uV curable (methyl) acrylate resin, moisture cured modification (methyl) acrylate resin, (methyl) vinylformic acid reactive thinner, moisture cured (methyl) vinylformic acid reactive thinner, light trigger, catalyzer; By suitable formula rate, prepare UV/ moisture dual cure laminated adhesive;

Below be the embodiment that the contriver provides, but the present invention is not limited to these embodiment;

Preparing method: accurately weigh various raw materials by formula rate, produce UV/ moisture dual cure laminated adhesive, tensile strength, elongation at break and the hardness of testing glue surface drying energy, wet solid surface drying time and cured glue body according to aforesaid preparation technology;

Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further detailed description, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. UV/ moisture dual cure laminated adhesive is characterized in that said laminated adhesive is formed as follows by weight:

Acrylate resin 0～50

Moisture cured modified acrylic ester resin 0～50

Vinylformic acid reactive thinner 10～40

Moisture cured modified acroleic acid reactive thinner 10～40

Light trigger 0～10

Catalyzer 0～2

Said acrylate resin is one or more the mixture in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate and the modifier thereof;

Said moisture cured modification (methyl) acrylate resin general formula is following:

Wherein: m, n are respectively 1～4 integer, and R1 is acrylate group or methacrylate based group, and R2 is the moisture cured group that comprises NCO group or siloxane groups;

Said vinylformic acid reactive thinner is one or more the mixture in triglycerin diacrylate, triglycerin dimethyl propylene acid esters, ethoxyquin triglycerin diacrylate, THF propenoate, 1,6 hexanediol diacrylate, the third oxidation USP Kosher triacrylate, IBOA, isobornyl methacrylate, the 2-phenoxyethyl acrylate;

Said moisture cured modified acroleic acid reactive thinner general formula is following:

Wherein: a, b are respectively 1～3 integer, and R3 is acrylate group or methacrylate based group, and R4 is the moisture cured group that comprises NCO group or siloxane groups.

2. UV/ moisture dual cure laminated adhesive according to claim 1; It is characterized in that; Said acrylate resin comprises the methacrylate resin that it is corresponding; Said moisture cured modified acrylic ester resin comprises the moisture cured modified methyl acrylic resin that it is corresponding; Said moisture cured modified acroleic acid reactive thinner comprises the moisture cured modified methacrylic acid reactive thinner that it is corresponding, and said epoxy acrylate comprises that its corresponding epoxy methacrylates, said urethane acrylate comprise that its corresponding urethane methacrylate, said polyester acrylate comprise that its corresponding polyester methacrylate, said polyether acrylate comprise polyethers methacrylic ester and modifier thereof that it is corresponding.

3. UV/ moisture dual cure laminated adhesive according to claim 1 and 2; It is characterized in that; Said laminated adhesive also comprises other additives of 0～2 part, and said other additives are one or more the mixture in pigment, skimmer, flow agent, wetting agent, the dispersion agent.

4. UV/ moisture dual cure laminated adhesive according to claim 3; It is characterized in that; Said light trigger is 2-hydroxyl-aminomethyl phenyl propane-1-ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, benzoin dimethylether, UVNUL MS-40, contraposition N, the different monooctyl ester of N-dimethylaminobenzoic acid, 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, the mixture of one or more in the 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester;

Said catalyzer is one or more the mixture in positive isopropyl titanate, tetrabutyl titanate, ethylacetoacetate titanium mixture, metatitanic acid four tert-butyl ester mixtures, two LAURIC ACID 99 MIN tin methides, the methyl aceto acetate tin composite.

5. preparation is characterized in that like the method for the described UV/ moisture of claim 1～4 dual cure laminated adhesive said method is made up of following steps successively:

(a) acrylate resin, moisture cured modified acrylic ester resin, vinylformic acid reactive thinner, moisture cured modified acroleic acid reactive thinner mixed 10～60 minutes under high temperature, lucifuge, vacuum condition;

(b) adding light trigger mixed 10～60 minutes under room temperature, lucifuge, vacuum condition;

(c) add catalyzer, other additives, under room temperature, lucifuge, vacuum condition 10～60 minutes, it is uniformly dispersed.

6. method according to claim 5; It is characterized in that; Said acrylate resin comprises that its corresponding methacrylate resin, said moisture cured modified acrylic ester resin comprise the moisture cured modified methyl acrylic resin that it is corresponding, and said vinylformic acid reactive thinner comprises that its corresponding methylacrylic acid reactive thinner, said moisture cured modified acroleic acid reactive thinner comprise the moisture cured modified methacrylic acid reactive thinner that it is corresponding.