Ultraviolet-cured glass fabric impregnated reinforced material as well as preparation method and application thereof

Abstract

The invention discloses an ultraviolet-cured glass fabric impregnated reinforced material as well as a preparation method and application thereof. The ultraviolet-cured glass fabric impregnated reinforced material comprises the following components in parts by weight: 50-70 parts of main body UV resin; 10 to 15 parts of tripropylene glycol diacrylate; 10 to 15 parts of N-acryloyl morpholine; 15 to 20 parts of cyclotrimethylolpropane methylal acrylate; and 5-10 parts of a photoinitiator. The prepared ultraviolet-cured glass fabric impregnated reinforced material has good cold and hot temperature difference resistance, high temperature resistance and weather resistance, also has good scratch resistance, can be used for processing glass fabric in a manner of photocuring after dip coating, and has the advantages of simple processing technology, high efficiency, low energy consumption and no pollution to the environment.

Description

Technical Field

[0001] The present invention relates to the technical field of fiberglass cloth impregnating materials, and particularly relates to an ultraviolet-curable fiberglass cloth impregnating reinforcing material, a preparation method thereof, and an application thereof. Background Art

[0002] Glass fiber (hereinafter referred to as fiberglass) is an excellent inorganic non-metallic material, commonly used as a reinforcing material, an electrical insulating material, a heat insulating material, and a circuit board substrate in composite materials in various fields of the national economy. Among them, electronics, transportation, and construction are the three main application fields.

[0003] Fiberglass is an important raw material in the insulation material industry. It mainly serves as a base material in insulation materials and also plays a reinforcing role. Among the six major categories of insulation materials, the main products using fiberglass and its products include impregnated fiber products, laminated products, electrical plastic products, mica products, etc. The main impregnated fiber products using fiberglass include: fiberglass varnished cloth, sleeves, non-woven binding tapes, prepreg materials, etc. The product manufacturing method is a soft insulating material made by using fiberglass cloth or other fiberglass products as the base material, impregnating or coating with synthetic resin, and then baking and drying. It has good mechanical strength, flexibility, and high dielectric properties. It is widely used in the coil wrapping, lining insulation, and wiring insulation of motors, electrical appliances, electrical instruments, and household appliances, and is also used in the manufacture of composite materials.

[0004] The impregnation process of a prepreg (semi-cured sheet) reinforced with glass fiber cloth is one of the key process technologies for producing semi-finished materials of copper clad laminates (CCL) and semi-cured substrates for multilayer boards. The traditional preparation method is to first add an organic solvent to reduce the viscosity of the adhesive solution to achieve wetting of the fiberglass cloth, and then heat to volatilize the solvent to cure the adhesive solution into a semi-cured sheet. The traditional solvent method for preparing semi-cured sheet CCL by impregnating fiberglass cloth not only brings environmental problems due to solvent volatilization, but also the solvent remaining in the adhesive solution affects the product performance. With the continuous improvement of environmental protection requirements and product performance, the use of a solvent-free impregnation method to prepare semi-cured sheets to overcome the environmental pollution caused by solvent volatilization and the problem that the residual solvent affects product performance has become a development trend, enabling the CCL industry to fundamentally solve environmental protection problems. Summary of the Invention

[0005] To overcome the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide an ultraviolet-curable fiberglass cloth impregnating reinforcing material, which is used as a fiberglass cloth reinforcing material, has good resistance to cold and heat temperature differences, high temperature resistance, and weather resistance, and also has good scratch resistance.

[0006] The present invention is achieved through the following technical solutions:

[0007] In the first aspect, the present invention provides an ultraviolet-curable fiberglass cloth impregnating reinforcing material, comprising the following components in parts by weight:

[0008]

[0009] Wherein, the main UV resin is made of the following components in parts by weight:

[0010]

[0011] Preferably, the molecular weight Mn of the main UV resin is 4000-8000. More preferably, the molecular weight Mn of the main UV resin is 6000-7000. The present invention has found through experimental research that the glass fiber cloth impregnated reinforcement material prepared from the main UV resin with a molecular weight within the above range has the characteristics of both hardness and toughness.

[0012] Preferably, the polycarbonate polyol is a mixture of one or more obtained by transesterifying dimethyl carbonate or diethyl carbonate with one or more of 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol, 3-methylpentanediol, and 1,4-cyclohexanedimethanol. The polycarbonate polyol of the present invention can be obtained by commercial means or by self-production through conventional synthesis methods.

[0013] Preferably, the diisocyanate is one or a mixture of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and cyclohexane dimethylene diisocyanate.

[0014] Preferably, the hydroxyacrylate is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate, or a mixture of several of them.

[0015] Preferably, the photoinitiator is one or a mixture of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate or isopropylthioxanthone.

[0016] Preferably, the UV-cured glass fiber cloth impregnated reinforcement material further comprises, by weight, 10-20 parts of filler, 0.05-0.2 parts of anti-settling agent, and 0.05-0.2 parts of defoaming agent.

[0017] Preferably, the filler is talcum powder of 400-600 mesh; the anti-settling agent is fumed silica; and the defoaming agent is a polymer solution containing silicone.

[0018] Second aspect, the present invention also provides a method for preparing the above-mentioned ultraviolet-curable glass fiber cloth impregnating reinforcing material, comprising the following steps:

[0019] (1) Preparation of the main body UV resin:

[0020] By weight, 50 - 70 parts of polycarbonate polyol, 20 - 30 parts of diisocyanate, and 0.02 - 0.5 part of catalyst are added to a reaction vessel, heated to 60 - 70 °C, the reaction temperature is controlled at 60 - 70 °C, and kept warm until the NCO value reaches the theoretically calculated value. Then, 10 - 15 parts of hydroxyacrylate and 0.02 - 0.5 part of inhibitor are added, heated to 75 - 85 °C, the reaction temperature is controlled at 75 - 85 °C, and kept warm until the NCO value is 0. The total reaction time is 3 - 6 hours, and the product is discharged to obtain the main body UV resin;

[0021] (2) Preparation of the ultraviolet-curable glass fiber cloth impregnating material:

[0022] Add 50 - 70 parts of the main body UV resin, 10 - 15 parts of tripropylene glycol diacrylate, 10 - 15 parts of N - acryloylmorpholine, and 15 - 20 parts of trimethylolpropane formal acrylate. While stirring, add 5 - 10 parts of photoinitiator, disperse for 1 - 2 hours, remove bubbles under vacuum, and filter to obtain the product.

[0023] In the method for synthesizing the main body UV resin of the present invention, first reacting polycarbonate polyol with diisocyanate can ensure the sufficiency of the reaction between the reaction groups of the polyol and the reaction groups of the diisocyanate, the molecular weight of the obtained product is relatively close to the designed molecular weight, and there are fewer small molecule by-products in the product.

[0024] Preferably, the catalyst is one or a mixture of several of triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, dibutyltin dilaurate, and dibutyltin diacetate.

[0025] Preferably, the inhibitor is one or a mixture of several of p - methoxyphenol, hydroquinone, 2 - tert - butylhydroquinone, or 2,5 - di - tert - butylhydroquinone.

[0026] Third aspect, the present invention also provides the application of the above-mentioned ultraviolet-curable glass fiber cloth impregnating reinforcing material in the preparation of semi-finished materials for copper clad laminates and semi-cured base materials for multi-layer boards.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The main body of the UV resin of the present invention is modified by polycarbonate to obtain a polyurethane acrylate prepolymer containing polycarbonate segments. The introduction of the polycarbonate segments has a high internal cohesive energy due to the presence of a large number of carbonate bonds in the molecule, excellent mechanical properties, high strength, and good resistance to temperature difference between hot and cold and weather resistance.

[0029] (2) By using tripropylene glycol diacrylate, N-acryloylmorpholine, and trimethylolpropane formal acrylate in combination, the material has very little irritation to the skin, low odor, low volume shrinkage, and excellent flexibility; good deep curing and excellent high-temperature resistance.

[0030] (3) The ultraviolet-curable fiberglass cloth impregnating and reinforcing material provided by the present invention uses a polyurethane acrylate prepolymer containing polycarbonate segments as the main body UV resin, in combination with acrylic monomers and other additives. The material is coated on the fiberglass cloth by impregnation processing and cured by a UV high-pressure mercury lamp, and can be quickly formed into a fiberglass cloth reinforcing material with much higher strength than the pure fiberglass cloth. The processing process is simple, with high efficiency, low energy consumption, and no pollution to the environment. Specific embodiments

[0031] The present invention will be further described below through specific embodiments. The following examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples.

[0032] The raw materials used in the present invention are all commercially available, as follows:

[0033] Polycarbonate polyol: Ube Industries, Ltd. UC90 in Japan;

[0034] Polyether polyol: Sanyo PEG2000 in Japan;

[0035] Polyester polyol: Asahi Kasei Chemicals XCP2000;

[0036] Diisocyanate: Wanhua Chemical IPDI;

[0037] Hydroxy acrylate: Jinan Hongteng Weiye New Materials HEA;

[0038] Catalyst: Dibutyltin dilaurate;

[0039] Polymerization inhibitor: p-methoxy phenol, hydroquinone;

[0040] Polyurethane acrylate: Changxing Chemical Industry 6112-100;

[0041] Tripropylene glycol diacrylate: Changxing Chemical Industry EM223;

[0042] N-acryloylmorpholine: Suihua Biotechnology Co., Ltd. ACMO;

[0043] Trimethylolpropane formal acrylate: Changxing Chemical Industry EM212;

[0044] Tetrahydrofurfuryl acrylate: Changxing Chemical Industry EM214;

[0045] Filler: 400 - mesh talc powder;

[0046] Photoinitiator: 184;

[0047] Anti - settling agent: AFCONA 4000;

[0048] Defoaming agent: AFCONA 2035.

[0049] Preparation of the main body UV resin:

[0050] According to the formula shown in Table 1, add polyol, diisocyanate, and catalyst to the reaction vessel, heat to 60 - 70 °C, control the reaction temperature at 60 - 70 °C, keep warm until the NCO value reaches the theoretically calculated value, then add hydroxyacrylate and inhibitor, heat to 75 - 85 °C, control the reaction temperature at 75 - 85 °C, keep warm until the NCO value is 0, the total reaction time is 5 hours, and discharge to obtain the main body UV resin;

[0051] Table 1 A1 - A3 Main body UV resin (parts by weight)

[0052]

[0053]

[0054] Examples 1 - 3

[0055] According to the formula shown in Table 2, add the main body UV resin A1, tripropylene glycol diacrylate EM223, N - acryloylmorpholine ACMO, trimethylolpropane formal acrylate EM212, stir and add the photoinitiator 184, anti - settling agent 4000, defoaming agent 2035, then add the filler 400 - mesh talc powder while stirring, disperse for 1 hour, remove air bubbles under vacuum, filter, and obtain. After this material is impregnated and coated on the fiberglass cloth and then cured by a UV high - pressure mercury lamp, it is formed into a fiberglass cloth - reinforced material, and its various properties are tested. The results are shown in Table 2.

[0056] Comparative Example 1

[0057] The difference between this comparative example and Example 1 is that polyether polyol PEG2000 is used to replace polycarbonate polyol UC90 to synthesize the main body UV resin A2.

[0058] Comparative Example 2

[0059] The difference between this comparative example and Example 1 is that polyester polyol XCP2000 is used to replace polycarbonate polyol UC90 to synthesize the main body UV resin A3.

[0060] Comparative Example 3

[0061] The difference between this comparative example and Example 1 is that polyurethane acrylate 6112-100 from Changxing Chemical Industry is used to replace the main body UV resin A1.

[0062] Comparative Example 4

[0063] The difference between this comparative example and Example 1 is that ACMO is not added to the formulation.

[0064] Comparative Example 5

[0065] The difference between this comparative example and Example 1 is that EM223 is not added to the formulation.

[0066] Comparative Example 6

[0067] The difference between this comparative example and Example 1 is that EM214 from Changxing Chemical Industry is used to replace EM212.

[0068] Comparative Example 7

[0069] The difference between this comparative example and Example 1 is that the main body UV resin is prepared by a one-step method, specifically as follows:

[0070] 60 parts of polycarbonate polyol UC90, 25 parts of diisocyanate IPDI, 15 parts of hydroxy acrylate HEA, 0.1 part of p-methoxy phenol, 0.05 part of hydroquinone, and 0.1 part of dibutyltin dilaurate are added to a reaction vessel, heated to 75-85 °C, the reaction temperature is controlled at 75-85 °C, and kept warm until the NCO value is 0. The total reaction time is 5 hours, and the product is discharged to obtain the main body UV resin B;

[0071] The rest is the same as Example 1.

[0072] Table 2 Composition and performance results of each component in the examples and comparative examples (parts by weight)

[0073]

[0074]

[0075] As can be seen from the results of the examples in Table 2, using a polyurethane acrylate prepolymer containing a polycarbonate segment as the main body UV resin, the glass fiber cloth impregnated reinforcing material prepared has high strength, high toughness, and good resistance to temperature difference between cold and heat, high temperature, and weather resistance.

[0076] Compared with Example 1, in Comparative Example 1, polyether polyol PEG2000 was used to replace polycarbonate polyol UC90 to synthesize the main body UV resin. The weather resistance of the prepared fiberglass cloth impregnated reinforcing material became worse. After 7 days of the double 85 test, bubbles appeared on the surface and it became sticky.

[0077] Compared with Example 1, in Comparative Example 2, polyester polyol XCP2000 was used to replace polycarbonate polyol UC90 to synthesize the main body UV resin. Both the cold and heat temperature difference resistance performance and the high temperature resistance performance of the prepared fiberglass cloth impregnated reinforcing material decreased.

[0078] Compared with Example 1, in Comparative Example 3, polyurethane acrylate 6112-100 from Changxing Chemical was used to replace the main body UV resin A1. The scratch resistance of the prepared fiberglass cloth impregnated reinforcing material decreased to grade B4; the weather resistance also became worse, and bubbles appeared on the surface after 7 days of the double 85 test.

[0079] Compared with Example 1, in Comparative Example 4, ACMO was not added to the formula. The high temperature resistance of the prepared fiberglass cloth impregnated reinforcing material became worse. After being placed in a high temperature oven at 120 °C for 7 days, cracking occurred.

[0080] Compared with Example 1, in Comparative Example 5, EM223 was not added to the formula. The scratch resistance of the prepared fiberglass cloth impregnated reinforcing material decreased to grade B5, and the high temperature resistance also became worse. After being placed in a high temperature oven at 120 °C for 7 days, cracking occurred. It shows that the combined use of tripropylene glycol diacrylate, N-acryloylmorpholine, and trimethylolpropane formal acrylate has a synergistic effect and has excellent flexibility; the deep curing is good and it has good high temperature resistance.

[0081] Compared with Example 1, in Comparative Example 6, EM214 from Changxing Chemical was used to replace EM212. The scratch resistance of the prepared fiberglass cloth impregnated reinforcing material decreased to grade B5 and became very poor; the weather resistance also became worse, and bubbles appeared on the surface after 7 days of the double 85 test.

[0082] Compared with Example 1, in Comparative Example 7, the main body UV resin B synthesized by the one-step method in Comparative Example 7 had a molecular weight Mn of only 1168. Both the cold and heat temperature difference resistance performance and the high temperature resistance performance of the prepared fiberglass cloth impregnated reinforcing material decreased.

[0083] Each performance test method or standard:

[0084] High and low temperature cycle test for 7 days: GB / T 4893.7-2013 Determination method for resistance of furniture surface paint film to cold and heat temperature difference.

[0085] Scratch resistance test method: EN 16094 Laminate floor coverings. Test method for determination of resistance to micro-scratches.

[0086] Double 85 test for seven days: GB / T 2423.50-2012 environmental test method.

[0087] Resistant to 120℃ high temperature: placed in a 120℃ high temperature oven for seven days to test whether it cracks.

Claims

1. A UV-cured glass fiber cloth impregnated reinforcement material, characterized in that: The composition comprises the following components in parts by weight: Main UV resin 50-70 parts Tripropylene glycol diacrylate 10-15 parts N-Acryloylmorpholine 10-15 parts 15-20 parts of cyclotrimethylolpropane formal acrylate 5-10 parts of photoinitiator; Wherein, the main UV resin is made of the following components in parts by weight: Polycarbonate polyol 50-70 parts 20-30 parts of diisocyanate Hydroxyacrylate 10-15 parts.

2. The UV-cured glass fiber cloth impregnated reinforcement material according to claim 1, characterized in that: The molecular weight Mn of the main UV resin is 4000-8000, and more preferably the molecular weight Mn is 6000-7000.

3. The UV-cured glass fiber cloth impregnated reinforcement material according to claim 1, characterized in that: The polycarbonate polyol is one or a mixture of dimethyl carbonate or diethyl carbonate obtained by transesterification with one or more of 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol, 3-methylpentanediol and 1,4-cyclohexanedimethanol.

4. The UV-cured glass fiber cloth impregnated reinforcement material according to claim 1, characterized in that: The diisocyanate is one or a mixture of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or cyclohexane dimethylene diisocyanate.

5. The UV-cured glass fiber cloth impregnated reinforcement material according to claim 1, characterized in that: The hydroxy acrylate is one or a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or hydroxybutyl acrylate.

6. The UV-cured glass fiber cloth impregnated reinforcement material according to claim 1, characterized in that: The photoinitiator is one or a mixture of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate or isopropylthioxanthone.

7. The UV-cured glass fiber cloth impregnated reinforcement material according to claim 1, characterized in that: By weight, the ultraviolet light-cured glass fiber cloth impregnated reinforcement material further comprises 10-20 parts of filler, 0.05-0.2 parts of anti-settling agent, and 0.05-0.2 parts of defoaming agent.

8. The ultraviolet light-cured glass fiber cloth impregnated reinforcement material according to claim 7, characterized in that: The filler is talcum powder with a mesh size of 400-600; the anti-settling agent is fumed silicon dioxide; and the defoaming agent is a polymer solution containing organic silicon.

9. The method for preparing the ultraviolet light-cured glass fiber cloth impregnated reinforcement material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Preparation of main UV resin: 50-70 parts of polycarbonate polyol, 20-30 parts of diisocyanate and 0.02-0.5 parts of catalyst are added to a reaction container by weight, heated to 60-70°C, the reaction temperature is controlled at 60-70°C, and the temperature is kept until the NCO value reaches the theoretical calculated value, and then 10-15 parts of hydroxy acrylate and 0.02-0.5 parts of polymerization inhibitor are added, heated to 75-85°C, the reaction temperature is controlled at 75-85°C, and the temperature is kept until the NCO value is 0. The whole reaction time is 3-6 hours, and the main UV resin is obtained by discharging; (2) Preparation of UV-cured fiberglass cloth impregnated material: Add 50-70 parts of main UV resin, 10-15 parts of tripropylene glycol diacrylate, 10-15 parts of N-acryloylmorpholine, 15-20 parts of cyclotrimethylolpropane formal acrylate, add 5-10 parts of photoinitiator while stirring, disperse for 1-2 hours, remove bubbles in vacuum, filter to obtain.

10. Use of the ultraviolet light-cured glass fiber cloth impregnated reinforcement material according to any one of claims 1 to 8 in the preparation of semi-finished copper-clad laminate materials and semi-cured substrates for multilayer boards.

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