阅读说明：本技术 封边材料、制备方法及其应用 (Edge sealing material, preparation method and application thereof ) 是由 唐洋 孙超 苟金龙 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种封边材料、制备方法及其应用,属于材料封装领域。封边材料包括：30-150份聚氨酯树脂,0.1-50份UV单体和0.01-10份引发剂,以及所述封边材料的制备方法及其在电子级玻璃纤维布或纺织布中的应用,所述封边材料生产效率高、能耗低,具有良好的耐黄变性能,没有VOC产生,具有环境友好性,所述封边材料应用于电子级玻璃纤维布或纺织布封边后,所述电子级玻璃纤维布或纺织布的边缘仍具有极佳的柔韧性以及耐溶剂性能。(The invention discloses an edge sealing material, a preparation method and application thereof, and belongs to the field of material packaging. The edge sealing material comprises: 30-150 parts of polyurethane resin, 0.1-50 parts of UV monomer and 0.01-10 parts of initiator, and a preparation method and application thereof in electronic-grade glass fiber cloth or textile cloth of the edge sealing material, wherein the edge sealing material has high production efficiency, low energy consumption, good yellowing resistance, no VOC (volatile organic compounds) generation and environmental friendliness, and after the edge sealing material is applied to edge sealing of the electronic-grade glass fiber cloth or textile cloth, the edge of the electronic-grade glass fiber cloth or textile cloth still has excellent flexibility and solvent resistance.)

1. The edge sealing material is characterized by comprising the following components in parts by weight: 30-150 parts of polyurethane resin, 0.1-50 parts of UV monomer and 0.01-10 parts of initiator.

2. An edge sealing material according to claim 1, wherein the polyurethane resin is selected from a monofunctional polyurethane resin and/or a difunctional polyurethane resin.

3. An edge sealing material according to claim 2, wherein the difunctional polyurethane resin is obtained by reacting a difunctional diisocyanate monomer, a polyester polyol, a blocking agent and a catalyst;

or, the monofunctional polyurethane resin is obtained by reacting a monofunctional isocyanate monomer, a polyester polyol and the catalyst.

4. An edge sealing material according to claim 3, wherein the difunctional diisocyanate monomer is an aromatic difunctional diisocyanate monomer or an aliphatic difunctional diisocyanate monomer;

the monofunctional isocyanate monomer is 2-acryloxyethyl isocyanate.

5. An edge sealing material according to claim 3, wherein the polyester polyol is selected from one or more of polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran diol or polyethylene glycol.

6. An edge sealing material according to claim 3 wherein the blocking agent is selected from one or more of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.

7. The edge banding material of claim 3 wherein said catalyst is an organobismuth compound or an organotin compound.

8. An edge banding material as claimed in claim 7 wherein said organotin compound is selected from one of tetrabutyltin, tributyltin laurate and dibutyltin dilaurate.

9. An edge sealing material according to claim 1, wherein the UV monomer is selected from one or more of 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethoxyethoxyethyl acrylate, lauric acid acrylate, stearic acid acrylate, tripropylene glycol diacrylate, polyethylene glycol, diacrylate, ethoxylated bisphenol a, diacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethylacrylate, dipentaerythritol hexamethacrylate, ditrimethylolpropane tetramethacrylate.

10. The edge sealing material of claim 1 wherein the initiator is selected from one or more of a, a-dimethoxy-a-phenylacetophenone, 2-hydroxy-2-methyl-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, methyl benzoylformate, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, benzophenone, and 2-isopropylthioxanthone.

11. A method of making an edge banding material of claim 1, comprising:

according to the weight parts of the components, adding polyurethane resin, a UV monomer and an initiator, and uniformly mixing and stirring to obtain the edge sealing material.

12. Use of an edge banding material in an electronic grade fiberglass cloth or a woven cloth, wherein said use comprises applying the edge banding material of any of claims 1-10 to the edge banding of an electronic grade fiberglass cloth or a woven cloth.

Technical Field

The invention relates to the field of material packaging, in particular to an edge sealing material, a preparation method and application thereof.

Background

The electronic grade glass fiber is a basic raw material in the industries of electronic information, aerospace and the like, almost appears in each electronic component and is spread in various fields of national economy and national defense and military industry. Electronic grade glass fiber cloth woven by electronic grade glass fibers is an indispensable basic material for the Copper Clad Laminate (CCL) and Printed Circuit Board (PCB) industries, and the performance of the electronic grade glass fiber cloth determines important performances such as electrical performance, mechanical performance, dimensional stability and the like of the CCL and the PCB to a great extent. In the process of using the electronic-grade glass fiber cloth, in order to reduce the loss of raw materials and the pollution of waste leftover materials to the environment, edge sealing materials are often adopted to carry out edge sealing treatment on the cloth edges of the electronic-grade glass fiber cloth.

The edge sealing material provided by the related art comprises the following components: 35% -50% of bisphenol A type waterborne epoxy resin; 3% -7% of curing agent melamine; 1-3% of a treating agent silane coupling agent; the balance of water is 61-40%.

However, since the edge sealing material comprises the silane coupling agent with amino functional groups, the substance and the epoxy resin can generate chemical reaction at normal temperature, and the storage of products is not facilitated; and because the epoxy resin is adopted, the problems of easy yellowing in high temperature and brittleness after curing exist.

Disclosure of Invention

The invention provides an edge sealing material, a preparation method and application thereof, which can solve the problems that in the related technology, the edge sealing material can generate chemical reaction with epoxy resin at normal temperature, and is not beneficial to product storage; and because the epoxy resin is adopted, the problems of easy yellowing in high temperature and brittleness after curing exist. The technical scheme is as follows:

on one hand, the invention provides an edge sealing material which comprises the following components in parts by weight: 30-150 parts of polyurethane resin, 0.1-50 parts of UV monomer and 0.01-10 parts of initiator.

Optionally, the polyurethane resin is a monofunctional polyurethane resin and/or a difunctional polyurethane resin.

Optionally, the difunctional polyurethane resin is obtained by reacting a difunctional diisocyanate monomer, a polyester polyol, a blocking agent and a catalyst;

specifically, the polyurethane resin is prepared by the following method:

taking 50-300 parts of bifunctional diisocyanate monomer, 50-200 parts of end-capping reagent and 0.1-5 parts of catalyst, stirring and reacting for 0.5-10h under the condition of ice-water bath, introducing dry air during stirring, dropwise adding 1000 parts of polyester polyol, gradually heating to 40-100 ℃, and preserving heat for 5-20h to obtain the bifunctional polyurethane resin.

Alternatively, the monofunctional polyurethane resin is obtained by reacting a monofunctional isocyanate monomer, a polyester polyol and a catalyst.

Specifically, the monofunctional polyurethane resin is prepared by the following method:

taking 50-150 parts of monofunctional isocyanate monomer and 0.1-1 part of catalyst, heating to 40-100 ℃, stirring, introducing dry air, after the temperature is stable, dropwise adding 1000 parts of 100-one polyester polyol, and preserving the heat for 2-15 hours to obtain the polyurethane resin.

Optionally, the difunctional diisocyanate monomer is an aromatic difunctional diisocyanate monomer or an aliphatic difunctional diisocyanate monomer;

the monofunctional isocyanate monomer is 2-acryloxyethyl isocyanate.

Optionally, the polyester polyol is selected from one or more of polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran diol, or polyethylene glycol.

Optionally, the blocking agent is selected from one or more of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.

Alternatively, the catalyst is an organobismuth compound or an organotin compound.

Alternatively, the organotin compound is selected from one of tetrabutyltin, tributyltin laurate and dibutyltin dilaurate.

Optionally, the UV monomer is selected from one or more of 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethoxyethoxyethyl acrylate, lauric acrylate, stearic acrylate, tripropylene glycol diacrylate, polyethylene glycol, diacrylate, ethoxylated bisphenol a, diacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethylacrylate, dipentaerythritol hexamethacrylate, ditrimethylolpropane tetramethacrylate.

Optionally, the initiator is selected from one or more of a, a-dimethoxy-a-phenylacetophenone), 2-hydroxy-2-methyl-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl methanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, methyl benzoylformate, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, benzophenone, 2-isopropylthioxanthone.

In another aspect, the present invention provides a method for preparing an edge sealing material, the method being used for preparing any one of the edge sealing materials described above, and the method including:

adding the photocuring polyurethane resin, the UV monomer and the initiator according to the parts by weight of the components, and uniformly mixing and stirring to obtain the edge sealing material.

In still another aspect, the present invention provides an edge banding material for electronic grade fiberglass cloth or textile cloth, wherein the application comprises applying any one of the edge banding materials described above to the edge banding of the electronic grade fiberglass cloth or textile cloth.

The technical scheme provided by the invention can at least bring the following beneficial effects:

according to the edge sealing material, unsaturated bonds in polyurethane resin are broken through ultraviolet or visible light irradiation, and free radicals are generated; the initiator is heated and decomposed under the irradiation of ultraviolet rays or visible light, and the UV monomer and free radicals generated by the polyurethane resin are initiated to perform a crosslinking reaction, so that the polyurethane resin is rapidly crosslinked and cured, and the edge sealing of the electronic-grade glass fiber cloth or the textile cloth is realized. The edge sealing material avoids the use of solvents, can be cured by light, does not need baking, and has high production efficiency and low energy consumption. Because the preparation raw materials of the edge sealing material do not contain aromatic compounds, the yellowing resistance of the product is improved. The light curing equipment is low in investment, so that a large amount of investment is saved, the environmental pollution is reduced, the resources are saved, no VOC (volatile organic compounds) is generated, the environment-friendly performance is realized, the edge sealing material disclosed by the invention has excellent flexibility after being cured, and based on the optimized selection of the content proportion of each component in the edge sealing material, the material cured by the edge sealing material disclosed by the invention has excellent solvent resistance, the problem that the edge sealing material falls off or is corroded cannot occur even after being contacted with an organic solvent, and particularly, the edge sealing material disclosed by the invention is particularly suitable for edge sealing of electronic grade glass fiber cloth due to the excellent solvent resistance.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.

In a first aspect, the invention provides an edge sealing material, which comprises the following components in parts by weight:

30-150 parts of polyurethane resin, 0.1-50 parts of UV monomer and 0.01-10 parts of initiator;

the polyurethane resin is a monofunctional polyurethane resin and/or a difunctional polyurethane resin.

In some embodiments of the invention, the isocyanate monomer is a monofunctional isocyanate or a difunctional diisocyanate.

The bifunctional polyurethane resin is prepared by the following method:

taking 50-300 parts of bifunctional diisocyanate monomer, 50-200 parts of end-capping reagent and 0.1-5 parts of catalyst, stirring and reacting for 0.5-10h under the condition of ice-water bath, and introducing dry air in the stirring process;

dripping 100 and 1000 parts of polyester polyol, gradually heating to 40-100 ℃, and preserving heat for 5-20h to obtain bifunctional polyurethane resin;

alternatively, the monofunctional polyurethane resin is prepared by the following method:

taking 50-150 parts of monofunctional isocyanate monomer and 0.1-1 part of catalyst, heating to 40-100 ℃, stirring and introducing dry air;

after the temperature is stable, 100-1000 parts of polyester polyol is dripped, and the heat is preserved for 2-15h to obtain the single-functionality polyurethane resin.

Under the irradiation of ultraviolet rays or visible light, unsaturated bonds in the polyurethane resin are broken to generate free radicals; the initiator is heated and decomposed under the irradiation of ultraviolet rays or visible light, and the UV monomer and free radicals generated by the polyurethane resin are initiated to perform a crosslinking reaction, so that the polyurethane resin is rapidly crosslinked and cured, and the edge sealing of the electronic-grade glass fiber cloth is realized.

The edge sealing material provided by the embodiment of the invention avoids the use of solvents, can be cured by light and does not need baking, so that the production efficiency of the edge sealing material is high and the energy consumption is low. Because the preparation raw materials of the edge sealing material do not contain aromatic compounds, the yellowing resistance of the product is improved. And the investment of the light curing equipment is low, so that a large amount of investment is saved, the environmental pollution is reduced, the resources are saved, no VOC (volatile organic compounds) is generated, and the light curing equipment is environment-friendly.

The embodiments of the invention will be further explained and illustrated below.

In some embodiments of the invention, the edge banding material comprises 30-150 parts by weight of a polyurethane resin; 0.1-50 parts of UV monomer; 0.01-10 parts of initiator.

In some embodiments of the invention, the edge banding material comprises 40-150 parts by weight of a polyurethane resin; 0.1-40 parts of UV monomer; 0.01-5 parts of initiator.

In some embodiments of the invention, the edge banding material comprises 40-120 parts by weight of a polyurethane resin; 0.1-45 parts of UV monomer; 0.01-3 parts of initiator.

In some embodiments of the invention, the edge banding material comprises 45-110 parts by weight of a polyurethane resin; 0.1-35 parts of a UV monomer; 0.1-5 parts of initiator.

In some embodiments of the invention, the edge banding material comprises 40-100 parts by weight of a polyurethane resin; 1-30 parts of a UV monomer; 0.1-3 parts of initiator.

In some embodiments of the invention, the edge banding material comprises 45-100 parts by weight of a polyurethane resin; 1-25 parts of a UV monomer; 0.1-3 parts of initiator.

As an example, the polyurethane resin may be 30 parts, 31 parts, 35 parts, 40 parts, 41 parts, 42 parts, 43 parts, 45 parts, 50 parts, 55 parts, 65 parts, 70 parts, 75 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, or the like by weight.

The weight parts of the UV monomer may be 0.01 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 1 part, 1.5 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 20 parts, 30 parts, 40 parts, or 50 parts, etc.

The initiator may be present in an amount of 0.01 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like by weight.

As an example, the present invention provides a method for preparing a monofunctional polyurethane resin and a difunctional polyurethane resin.

The bifunctional polyurethane resin is obtained by reacting a bifunctional diisocyanate monomer, polyester polyol, a blocking agent and a catalyst;

specifically, the bifunctional polyurethane resin is prepared by the following method:

taking 50-300 parts of bifunctional diisocyanate monomer, 50-200 parts of end-capping reagent and 0.1-5 parts of catalyst, stirring and reacting for 0.5-10h under the condition of ice-water bath, introducing dry air during stirring, dropwise adding 1000 parts of polyester polyol, gradually heating to 40-100 ℃, and preserving heat for 5-20h to obtain the polyurethane resin.

Preferably, in the method for preparing the bifunctional polyurethane resin, the reaction temperature is preferably 40 to 90 ℃, more preferably 40 to 80 ℃, and still more preferably 40 to 70 ℃.

Preferably, in the preparation method of the bifunctional polyurethane resin, the heat preservation time is 5 to 18 hours, more preferably 5 to 12 hours, and still more preferably 6 to 12 hours.

Further, in the preparation method of the bifunctional polyurethane resin, the content of the bifunctional diisocyanate monomer may be 50 parts, 55 parts, 65 parts, 70 parts, 70.575 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 141.15 parts, 150 parts, 168.19 parts, 174.16 parts, 200 parts, 222.29 parts, 250 parts, 250.24 parts, 300 parts, or the like. The amount of capping agent may be 50 parts, 55 parts, 65 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 116.12 parts, 120 parts, 130 parts, 130.14 parts, 140 parts, 150 parts, 200 parts, or the like. The catalyst may be present in an amount of 0.1 part, 0.2 part, 0.3 part, 0.42 part, 0.4 part, 0.5 part, 0.6 part, 1 part, 3 parts, 4 parts, 5 parts, etc. The bifunctional diisocyanate monomer, the blocking agent and the catalyst are reacted for 0.5 to 10 hours, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3.5 hours, 4.5 hours, 55 hours, 6.5 hours, 7 hours, 8 hours, 9 hours, 10 hours and the like under the ice-water bath condition. And introducing dry air in the stirring process, dripping 100-1000 parts of polyester polyol, gradually heating to 40-100 ℃, and preserving heat for 5-20 hours to obtain the polyurethane resin. Illustratively, the amount of the polyester polyol may be 100-900 parts, 50-800 parts, etc. Specific addresses may be 100 parts, 110 parts, 120 parts, 130 parts, 132.5 parts, 140 parts, 200 parts, 300 parts, 400 parts, 550 parts, 600 parts, 700 parts, 800 parts, 900 parts, 1000 parts, and the like.

The reaction temperature may be 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, etc. The holding time may be: 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h and the like.

The monofunctional polyurethane resin is obtained by reacting a monofunctional isocyanate monomer, a polyester polyol and a catalyst.

Specifically, the monofunctional polyurethane resin is prepared by the following method:

taking 50-150 parts of monofunctional isocyanate monomer and 0.1-1 part of catalyst, heating to 40-100 ℃, stirring, introducing dry air, after the temperature is stable, dropwise adding 1000 parts of 100-one polyester polyol, and preserving the heat for 2-15 hours to obtain the polyurethane resin.

Preferably, in the method for preparing the monofunctional polyurethane resin, the reaction temperature is preferably 40 to 90 ℃, more preferably 40 to 80 ℃, and still more preferably 40 to 70 ℃.

Preferably, in the preparation method of the monofunctional polyurethane resin, the heat preservation time is 5 to 15 hours, more preferably 5 to 12 hours, and still more preferably 6 to 10 hours.

Further, in the method of preparing the monofunctional polyurethane resin, the monofunctional isocyanate monomer may be contained in an amount of 50 parts, 55 parts, 65 parts, 70 parts, 70.575 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 141.15 parts, 150 parts, or the like. The catalyst may be present in an amount of 0.1 part, 0.2 part, 0.25 part, 0.3 part, 0.45 part, 0.5 part, 0.6 part, 1 part, etc. Heating the monofunctional isocyanate monomer and the catalyst in parts by mass to 40-100 ℃, stirring, introducing dry air, after the temperature is stable, dropwise adding 1000 parts of the polyester polyol in 100 parts, and preserving the heat for 2-15 hours to obtain the monofunctional polyurethane resin. For example, the temperature may be raised to 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or the like. And (3) dropwise adding 100-1000 parts of polyester polyol, and keeping the temperature for 2-15h to obtain the monofunctional polyurethane resin. Illustratively, the amount of the polyester polyol may be 100-900 parts, 50-800 parts, etc. Specific addresses may be 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 250 parts, 550 parts, 600 parts, 700 parts, 800 parts, 900 parts, 1000 parts, and the like. The reaction temperature may be 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, etc. The holding time may be: 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and the like.

The monofunctional and bifunctional urethane resins contain unsaturated double bonds, and the unsaturated bonds in the urethane resins are cleaved by irradiation with ultraviolet light or visible light, and the resultant radicals are generated, thereby allowing crosslinking and curing.

By selecting the monofunctional or bifunctional isocyanate, the curing speed of the prepared polyurethane resin can be controlled on one hand, and the hardness of the prepared polyurethane resin can be controlled on the other hand, so that the curing speed and the flexibility of the edge sealing material can be controlled.

Alternatively, when the isocyanate is a monofunctional isocyanate, it may be one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hydrogenated diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), 1,5-Naphthalene Diisocyanate (NDI), dimethylbiphenyl diisocyanate (4,4 '-diisocyanate-3, 3' -dimethylbiphenyl, TODI), and Xylylene diisocyanate (m-Xylylene diisocyanate, XDI). Illustratively, the monofunctional isocyanate monomer may also be 2-acryloxyethyl isocyanate. Illustratively, the monofunctional 2-acryloyloxyethyl isocyanate may be a technical grade isocyanate monomer, preferably monofunctional 2-acryloyloxyethyl isocyanate produced by Japanese Showa Denko K.K.

Alternatively, when the isocyanate is a difunctional isocyanate, it may be selected from an aliphatic difunctional diisocyanate or an aromatic isocyanate. So that the yellowing resistance of the edge sealing material can be improved.

In some embodiments of the invention, the polyester polyol is selected from one or more of polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran diol, or polyethylene glycol.

According to the embodiment of the invention, the polyester polyol is selected, so that the solvent resistance and the mechanical property of the polyurethane resin can be improved. As an example, the polyester polyol may be selected from one or more of Polycaprolactone Polyol (PCL), polycarbonate Polyol (PCDL), polytetrahydrofuran diol, or polyethylene glycol. By selecting the polyester polyol, the yellowing resistance of the edge sealing material can be improved. It should be noted that when the edge banding material of the present invention has particularly high solvent resistance, the polymeric polyol is preferably selected from polycaprolactone polyols and polycarbonate diols.

In some embodiments of the present invention, the polycaprolactone polyol may be a diol having a molecular weight Mn of 530, may be a triol having a molecular weight Mn of 300, 550, 850, 950, and may be a tetraol having a molecular weight Mn of 1000. As an example, a diol having a molecular weight of 200, a triol having a molecular weight of 300, a tetraol having a molecular weight of 400, and the like, produced from xylonite, are preferable.

In some embodiments of the invention, the polycarbonate diol PCDL may be selected from diols having a molecular weight Mn of 500, 800, 1000 or 2000, preferably those having the product designation T5650, T5651 or T5652 from asahi chemical co.

In some embodiments of the invention, the capping agent is selected from one or more of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate.

In one of the methods for preparing the bifunctional polyurethane resin provided by the embodiment of the invention, the end-capping reagent is selected, and the activity of the terminal group in the polyurethane resin can be reduced through the end-capping reagent, so that the viscosity of the polyurethane resin is reduced, and the adhesive force between the polyurethane resin and the electronic glass fiber cloth is increased.

As an example, the end-capping reagent can be a mixture of four of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate, and the mixing ratio can be 1:1:1: 2. The mixing ratio of the 2-hydroxyethyl acrylate, the hydroxyethyl methacrylate and the hydroxypropyl acrylate may be 1:1: 2. A mixture of 2-hydroxyethyl acrylate and hydroxyethyl methacrylate may be used in a mixing ratio of 1: 2.

In some embodiments of the invention, the catalyst is an organobismuth compound or an organotin compound.

The catalyst may be a mixture of an organobismuth compound and an organotin compound, and the mixing ratio may be 1:1 to 2. Illustratively, the mixing ratio may be 1:1 or 1: 2.

In some embodiments of the invention, the organotin compound is selected from one of tetrabutyltin, tributyltin laurate and dibutyltin dilaurate.

The organotin compound may be exemplified by a mixture of three kinds of tetrabutyltin, tributyltin laurate and dibutyltin dilaurate, and the mixing ratio may be 1:1:1: 2. A mixture of tetrabutyltin and tributyltin laurate may be used in a mixing ratio of 1: 2.

In some embodiments of the invention, the UV monomer is selected from one or more of 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethoxyethoxyethoxyethyl acrylate, lauric acrylate, stearic acrylate, tripropylene glycol diacrylate, polyethylene glycol, diacrylate, ethoxylated bisphenol A, diacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethylacrylate, dipentaerythritol hexamethacrylate, ditrimethylolpropane tetramethacrylate mono-, di-and multifunctional monomers.

When the UV monomer provided by the embodiment of the invention is irradiated by ultraviolet light or visible light, the unsaturated bond in the polyurethane resin can be initiated to be broken, and crosslinking and curing are carried out.

The UV monomer provided in the embodiment of the present invention may be selected from the monomers listed above, and may be one or two or a mixture of a plurality of monomers, and the mixing ratio of the embodiment of the present invention to a plurality of monomers is not limited thereto.

In some embodiments of the invention, the initiator is selected from one or more of a, a-dimethoxy-a-phenylacetophenone, 2-hydroxy-2-methyl-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, methyl benzoylformate, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, benzophenone, 2-isopropylthioxanthone.

The initiator provided in the embodiment of the present invention may be selected from the monomers listed above, and may be one or two kinds of the initiators, or may be a mixture of a plurality of the initiators, and the mixing ratio of the embodiment of the present invention to a plurality of the initiators is not limited thereto.

The edge sealing material disclosed by the invention has excellent mechanical properties, good flexibility and good edge sealing effect, and meanwhile, the edge sealing material has excellent yellowing resistance, does not influence the appearance effect of the glass fiber cloth after being cured, and has excellent comprehensive properties. The edge sealing material disclosed by the invention also has excellent solvent resistance to acetone, butanone and DMF (dimethyl formamide), and furthermore, the glass fiber cloth using the edge sealing material disclosed by the invention does not influence the coating of a rear-end solvent type epoxy resin. The polyurethane material can be cured by light without baking, has high production efficiency, low energy consumption and relatively low investment on light curing equipment, thereby saving a large amount of investment, reducing pollution, saving resources, generating no VOC and having better environmental friendliness.

It should be noted that the edge sealing material provided by the invention can be applied to electronic-grade glass fiber cloth or textile cloth.

In another aspect, a method of making an edge banding material is provided, the method comprising:

adding the photocuring polyurethane resin, the UV monomer and the initiator according to the weight parts of the components, and uniformly mixing and stirring to obtain the edge sealing material.

In a further aspect, embodiments of the present invention provide an application of the edge sealing material in electronic-grade fiberglass cloth or textile cloth, which includes applying any one of the edge sealing materials described above in the edge sealing of the electronic-grade fiberglass cloth or textile cloth.

The edge sealing material provided by the embodiment of the present invention will be further described by alternative embodiments.

Example 1

Preparing a polyurethane resin:

70.575 parts of monofunctional 2-acryloyloxyethyl isocyanate and 0.2 part of catalyst (product code number is348) Placing the mixture into a 500ml four-neck flask, heating the mixture to 40 ℃, starting stirring and introducing dry air;

taking 132.5 parts of polycaprolactone diol with the molecular weight of 530, after the temperature is stable, dropwise adding the polycaprolactone diol into a four-neck flask by using a constant-pressure low-liquid funnel, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 5 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

preparing an edge sealing material:

mixing and stirring uniformly 50 parts of the prepared polyurethane resin, 10 parts of 1, 6-hexanediol diacrylate, 5 parts of pentaerythritol triacrylate and 1.2 parts of 184 (1-hydroxycyclohexyl phenyl ketone) to obtain a photocurable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, wherein the coating width is about 3-4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 1000mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 2

Preparing a polyurethane resin:

141.15 parts of monofunctional 2-acryloyloxyethyl isocyanate and 0.42 part of catalyst (product code number is348) Placing the mixture into a 1L four-mouth flask, heating to 60 ℃, starting stirring and introducing dry air;

taking 400 parts of polycarbonate diol with the molecular weight of 800, dropwise adding the polycarbonate diol into a four-neck flask by using a constant-pressure low-liquid funnel after the temperature is stable, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 8 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

the preparation of the edge sealing material of the invention comprises the following steps:

mixing and stirring 100 parts of the prepared polyurethane resin, 15 parts of ethoxylated trimethylolpropane triacrylate, 5 parts of pentaerythritol triacrylate and 3 parts of 1-hydroxycyclohexyl phenyl ketone uniformly to obtain a photocurable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, wherein the coating width is about 3-4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 800mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 3

Preparing a polyurethane resin:

placing 168.19 parts of bifunctional hexamethylene diisocyanate, 116.12 parts of hydroxyethyl acrylate and 0.5 part of organic bismuth catalyst into a 1L four-neck flask, starting stirring, introducing dry air, reacting for 2 hours under the condition of ice-water bath, and controlling the temperature of a reaction system to be below 20 ℃;

taking 400 parts of polycarbonate diol (PCDL) with the molecular weight of 800, dropwise adding the polycarbonate diol into a four-neck flask by using a constant-pressure low-liquid funnel, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 4 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

the preparation of the edge sealing material of the invention comprises the following steps:

taking 75 parts of the prepared polyurethane resin, 10 parts of 1, 6-hexanediol dimethacrylate, 5 parts of stearic acid acrylate and 1.5 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide, and uniformly mixing and stirring to obtain the light-curable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, wherein the coating width is about 3-4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 1000mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 4

Preparing a polyurethane resin:

putting 222.29 parts of bifunctional isophorone diisocyanate, 130.14 parts of hydroxyethyl methacrylate and 0.5 part of organic bismuth catalyst into a 1L four-neck flask, starting stirring, introducing dry air, reacting for 3 hours under the condition of ice-water bath, and controlling the temperature of a reaction system to be below 20 ℃;

respectively weighing 200 parts of polycarbonate diol PCDL with the molecular weight of 1000 and 300 parts of polycaprolactone diol with the molecular weight of 1000, uniformly mixing, dropwise adding the uniformly mixed dihydric alcohol into a four-neck flask by using a constant-pressure low-liquid funnel, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 8 hours after the dropwise adding is finished, and obtaining the 100% solid content light-curable polyurethane resin after the reaction is finished;

the preparation of the edge sealing material of the invention comprises the following steps:

mixing and stirring uniformly 80 parts of the prepared polyurethane resin, 10 parts of 1, 4-butanediol diacrylate, 5 parts of lauric acrylate and 2 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide to obtain a light-curable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, coating the glass fiber cloth with the width of about 3cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 1000mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 5

Preparation of a photocurable polyurethane resin:

placing 174.16 parts of bifunctional toluene diisocyanate, 116.12 parts of hydroxyethyl acrylate and 0.4 part of organic bismuth catalyst into a 1L four-neck flask, starting stirring, introducing dry air, reacting for 3 hours under the condition of ice-water bath, and controlling the temperature of a reaction system to be below 20 ℃;

taking 500 parts of polycaprolactone diol with the molecular weight of 1000, uniformly mixing, dropwise adding the polycaprolactone diol into a four-neck flask by using a constant-pressure low-liquid funnel, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 8 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

the preparation of the edge sealing material of the invention comprises the following steps:

taking 50 parts of the prepared polyurethane resin, 1 part of 1, 4-butanediol diacrylate and 0.5 part of phenyl bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide, and uniformly mixing and stirring to obtain the light-curable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, coating the glass fiber cloth with the width of about 4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 500mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 6

Preparing a polyurethane resin:

placing 250.24 parts of bifunctional diphenylmethane diisocyanate, 116.12 parts of hydroxyethyl acrylate and 0.4 part of organic bismuth catalyst into a 2L four-neck flask, starting stirring, introducing dry air, reacting for 2-3h under the condition of ice-water bath, and controlling the temperature of a reaction system to be below 20 ℃;

taking 1000 parts of polycarbonate diol with the molecular weight of 2000, uniformly mixing, dropwise adding the polycarbonate diol into a four-neck flask by using a constant-pressure low-liquid funnel, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 8 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

the preparation of the edge sealing material of the invention comprises the following steps:

taking 100 parts of the prepared polyurethane resin, 10 parts of neopentyl glycol diacrylate ethoxy ethyl acrylate and 1.8 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and uniformly mixing and stirring to obtain the photocurable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, coating the glass fiber cloth with the width of about 4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 1000mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 7

Preparing a polyurethane resin:

70.575 parts of monofunctional 2-acryloyloxyethyl isocyanate and 0.25 part of the mixture are takenCatalyst and process for preparing same348 is put into a 500ml four-mouth flask, heated to 60 ℃, stirred and introduced with dry air;

taking 250 parts of polytetrahydrofuran diol PTMEG1000 with the molecular weight of 1000, dropwise adding the polytetrahydrofuran diol into a four-neck flask by using a constant-pressure low-liquid funnel after the temperature is stable, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the temperature for 8 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

the preparation of the edge sealing material of the invention comprises the following steps:

mixing and stirring uniformly 50 parts of the prepared light-curable polyurethane resin, 10 parts of tripropylene glycol diacrylate, 5 parts of pentaerythritol triacrylate and 1.2 parts of 1-hydroxycyclohexyl phenyl ketone to obtain a light-curable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, coating the glass fiber cloth with the width of about 4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 1000mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Example 8

Preparation of a photocurable polyurethane resin:

141.15 parts of monofunctional 2-acryloyloxyethyl isocyanate and 0.45 part of catalyst (product code number is348) Placing the mixture into a 1L four-mouth flask, heating to 60 ℃, starting stirring and introducing dry air;

taking 500 parts of polyethylene glycol with the molecular weight of 1000, dropwise adding the polytetrahydrofuran dihydric alcohol into a four-neck flask by using a constant-pressure low-liquid funnel after the temperature is stable, controlling the temperature below 70 ℃ in the dropwise adding process, preserving the heat for 8 hours after the dropwise adding is finished, and finishing the reaction to obtain the light-curable polyurethane resin with the solid content of 100%;

the preparation of the edge sealing material of the invention comprises the following steps:

taking 50 parts of the prepared light-curable polyurethane resin, 10 parts of tripropylene glycol diacrylate, 5 parts of neopentyl glycol diacrylate ethoxy ethyl acrylate and 1.5 parts of 2-hydroxy-2-methyl-phenyl-1 acetone, and uniformly mixing and stirring to obtain a light-curable glass fiber edge sealing material;

dipping the prepared edge sealing material by using a brush with the width of about 2cm, uniformly brushing the edge sealing material on the two side edges of the glass fiber cloth, coating the glass fiber cloth with the width of about 4cm, and carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 1000mj/cm2, so as to obtain the glass fiber cloth coated with the edge sealing material.

Comparative example

Dipping and uniformly brushing epoxy resin on the edges of two sides of the glass fiber cloth by using a brush with the width of about 2cm, wherein the coating width is about 3-4cm, and arranging the coated glass fiber cloth in an oven at 170 ℃ for 10min to obtain the glass fiber cloth coated with the edge sealing material.

The glass fiber cloths obtained in examples 1 to 8 and comparative example 1 were subjected to performance tests under the same conditions, and the test results are shown in table 1:

TABLE 1

As can be seen from performance tests of examples 1-8 and comparative examples, the edge sealing material provided by the embodiment of the invention has excellent yellowing resistance and excellent flexibility, and meanwhile, the edge sealing material provided by the embodiment of the invention also has good DMF (dimethyl formamide), acetone and butanone solvent resistance and good epoxy resin wettability, so that the glass fiber cloth subjected to edge sealing by using the edge sealing material provided by the embodiment of the invention does not influence the coating of solvent type epoxy resin at the rear end of the glass fiber cloth, and the operation process of the rear end of the glass fiber cloth is simpler.

It should be noted that the performance tests performed by the inventive examples on the above examples 1 to 8 and comparative example 1 are as follows:

the performance parameter detection method comprises the following steps:

firstly, testing the performances of DMF (dimethyl formamide), acetone and butanone resistant to solvents:

cutting a piece of square glass fiber cloth with the width of 15cm by 15cm, dipping a certain amount of water-based material to be detected (about 1/3 of a brush is immersed in a sample to be detected) by using a clean brush, coating the water-based material to be detected on the surface of the glass fiber cloth, repeatedly brushing the water-based material for 2-3 times in the same coating area, ensuring that the water-based material permeates into the other side of the cloth, wherein the brushing area is about 3-5cm wide and 10-15cm long.

Clamping two ends of the upper part of the coated glass fiber cloth by using dovetail clips, vertically hanging the coated glass fiber cloth in an oven at 170 ℃, taking out the coated glass fiber cloth after baking for 10min, and naturally cooling the coated glass fiber cloth.

Cutting a square with the size of about 5 x 5cm in a coating area of the dried glass fiber cloth, weighing the mass of the square with the precision of 0.001 by using an electronic balance, marking as m1, placing the square in a beaker filled with DMF \ acetone \ butanone solvent, immersing the glass fiber cloth in the solvent, soaking the glass fiber cloth for 10min at room temperature, taking out the glass fiber cloth, vertically hanging the glass fiber cloth in a 105 ℃ oven for 10min, taking out the glass fiber cloth, weighing the dried glass fiber cloth again, marking the mass as m2, and calculating the weight loss percentage of the glass fiber cloth.

The calculation formula is as follows:

when the weight loss percentage is less than or equal to 2 percent, the solvent resistance of the edge sealing material passes the test; when the percentage weight loss of the edge banding material is greater than 2%, it indicates that the solvent resistance of the edge banding material failed the test.

Secondly, testing the wettability of the epoxy resin:

cutting a square glass fiber cloth of about 50 x 30cm, dipping a certain amount of edge sealing material to be detected (about 1/3 of a brush is immersed in a sample to be detected) by using a clean brush, coating the edge sealing material on the two side surfaces of the glass fiber cloth, and repeatedly brushing the same coating area for 2-3 times to ensure that the edge sealing material to be detected permeates into the other side of the cloth, wherein the brushing area is about 3-5cm wide and 10-15cm long.

And carrying out photocuring on the coated glass fiber cloth by using a UV curing machine, wherein the curing energy is 500-1000mj/cm 2.

And (3) coating and wrapping the tray by using a film, and pouring epoxy resin, wherein the amount of the epoxy resin in the tray is about 1-2cm deep.

And clamping the two ends of the upper part of the glass fiber cloth by using dovetail clamps, and soaking the glass fiber cloth into the epoxy resin, so that the front and back surfaces of the glass fiber cloth are uniformly coated.

And vertically hanging the glass fiber cloth coated with the epoxy resin in a 170 ℃ oven, taking out after 10min, and naturally cooling.

After the glass fiber cloth is coated with the epoxy resin, the epoxy resin has a flat surface and does not have the poor wetting phenomena of obvious shrinkage, edge exclusion, strand flow and the like, and the glass fiber cloth subjected to edge sealing by using the edge sealing material is considered to have a passing epoxy spreading performance, otherwise, the glass fiber cloth does not pass the passing epoxy spreading performance.

Yellowing Δ b test method: and (3) arranging the glass fiber coated with the edge sealing material in an oven at 170 ℃ for 10min, testing by using a color difference meter to obtain a delta b value, and observing the yellowing condition by naked eyes.

The flexibility test method comprises the following steps: and manually rolling the glass fiber to form a cylinder shape, and judging that the glass fiber is distributed without brittle fracture.

The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.