A high adhesive wear-resistant adhesive layer composition, its preparation method and application

Abstract

The application discloses a kind of high bonding wear-resistant glue layer compositions, its preparation raw materials include: vinyl ester resin, functional monomer, photosensitizer, diluent, polyisocyanate, its preparation method is simple, weigh vinyl ester resin, functional monomer, photosensitizer, diluent, polyisocyanate is fully mixed, namely obtained.The specific vinyl ester resin, functional monomer, composite photosensitizer, diluent, polyisocyanate are selected to be mixed so that the obtained glue layer has high bonding strength, scratch resistance and wear resistance, smaller shrinkage and aging resistance.The glue layer component is simple, curing speed is fast, efficiency is high, and the emergence of coating bottom layer curing, surface uncured problem can be avoided at the same time.In addition, process does not need organic solvent, and the pollution is small in curing process, and can be widely applied to glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen, metal plate surface protection.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of adhesive layer composition preparation, C09J201 / 06, and in particular to a high-adhesion wear-resistant adhesive layer composition and its preparation method and application. BACKGROUND

[0002] Ultraviolet light curing technology is a new technology developed in recent years, which has the advantages of fast curing speed, strong adhesion, simple curing conditions, green environmental protection, and can be widely used in the fields of coatings, inks, adhesives, etc. During production and transportation, optical components and electronic components need to be attached with a protective film on their exposed surfaces to prevent damage, and an important component of the required protective film material includes an adhesive layer. The light-curable adhesive layer is the first choice for people. However, the preparation process of the adhesive layer will be disturbed by factors such as oxygen and water vapor in the environment, resulting in the situation that the bottom layer of the coating is cured and the surface is not cured and sticky, and also making the shrinkage of the protective film larger and denaturing, ultimately affecting the hardness, adhesion strength and scratch and wear resistance of the adhesive protective film.

[0003] Patent CN201510599894.5 discloses a kind of ultraviolet light curing adhesive, including polyester acrylate oligomer, polyurethane acrylate, epoxy acrylate, active diluent and photoinitiator, the adhesive has lower viscosity, good wear resistance, anti-aging and weather resistance, but it is realized by the synergistic effect of ultraviolet light absorber, light stabilizer and antioxidant. Patent CN202010558123.2 discloses a kind of light-curable adhesive layer composition and its protective film, the preparation raw material includes epoxy acrylate, non-epoxy pre-polymer containing double bond and hydroxyl, photoinitiator, diluent and aliphatic or alicyclic isocyanate, the obtained adhesive layer composition can avoid the situation that the bottom layer of the coating is cured and the surface is not cured and sticky, has the advantages of anti-aging and small shrinkage, but the adhesive strength and hardness of the adhesive layer as a protective film still need to be further improved. SUMMARY

[0004] In order to solve the above problems, the first aspect of the present application provides a high-adhesion wear-resistant adhesive layer composition, the preparation raw material of which includes, by weight:

[0005] 10-20 parts of vinyl ester resin, 65-85 parts of functional monomer, 1-5 parts of photosensitizer, 15-25 parts of diluent, 2-6 parts of polyisocyanate;

[0006] As a preferred embodiment, the functional group of the vinyl ester resin is 1-4, and the acid value is ≤5 mgKOH / g; preferably, the functional group degree of the vinyl ester resin is 2, and the acid value is ≤1 mgKOH / g;

[0007] As a preferred embodiment, the functional monomer is selected from at least one of 6-hydroxyhexyl acrylate, SMND-309, 3-methyl-2-butenyl caffeate, (2E)-3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid (2E)-3,7-dimethyl-2,6-octadien-1-yl ester;

[0008] As a preferred embodiment, the functional monomer is 3-methyl-2-butenyl caffeate;

[0009] As a preferred embodiment, the photosensitizer is selected from at least one of cationic photosensitizer, radical photosensitizer; preferably, the photosensitizer is cationic photosensitizer, radical photosensitizer;

[0010] As a preferred embodiment, the weight ratio of the cationic photosensitizer to the radical photosensitizer is 1:0.4-0.5; preferably, the weight ratio of the cationic photosensitizer to the radical photosensitizer is 1:0.46;

[0011] As a preferred embodiment, the cationic photosensitizer is selected from at least one of diaryliodonium salt, triaryliodonium salt, alkyl iodonium salt, cumene hexafluorophosphate ferrate; preferably, the cationic photosensitizer is diaryliodonium salt; further preferably, the cationic photosensitizer is hexafluoroantimonate salt of diaryliodonium salt;

[0012] As a preferred embodiment, the radical photosensitizer is selected from at least one of benzil, alkylbenzophenone, acyl phosphine oxide, benzophenone; preferably, the radical is benzophenone; further preferably, the radical photosensitizer is benzophenone;

[0013] As a preferred embodiment, the diluent is selected from at least one of methyl methacrylate, butyl acrylate, methyl acrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate; preferably, the diluent is methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate;

[0014] As a preferred embodiment, the weight ratio of the methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate is 4-8:1:0.3-0.7:0.8-1.5; further preferably, the weight ratio of the methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate is 6.4:1:0.52:1.1;

[0015] As a preferred embodiment, the polyisocyanate is selected from at least one of dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, 1,6-hexane diisocyanate, heptane diisocyanate; preferably, the polyisocyanate is dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate;

[0016] As a preferred embodiment, the weight ratio of the dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate is 1:1-2.

[0017] The second aspect of the present application provides a preparation method of a high-adhesion wear-resistant adhesive layer composition.

[0018] The ethylene ester resin, functional monomer, photosensitizer, diluent and polyisocyanate are weighed and mixed thoroughly to obtain the adhesive layer composition.

[0019] The third aspect of the present application provides an application of the high-adhesion wear-resistant adhesive layer composition: it can be applied to the protection of the surface of glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen and metal plate.

[0020] Compared with the prior art, the present application has the following beneficial effects:

[0021] (1) In the present application, the ethylene ester resin and functional monomer are prepared into an adhesive layer composition through the addition of photosensitizer, diluent and polyisocyanate for photocuring, and the obtained adhesive layer has high bonding strength, scratch and wear resistance, small shrinkage rate and aging resistance, and the cationic photosensitizer and free radical photosensitizer are used in combination, which avoids the inhibition of oxygen on the free radical photosensitizer and the sensitivity of cationic polymerization to water, improves the curing rate and adhesion, and improves the coating film performance.

[0022] (2) The epoxy acrylate keeps the excellent water resistance, toughness and adhesive properties of the epoxy resin, and meanwhile, can realize excellent curing type and formability by the photocuring method. However, the present applicant has unexpectedly found that the functional group of the added vinyl ester resin is 1-4, and the acid value is ≤5 mgKOH / g; in particular, the functional group of the vinyl ester resin is 2, and the acid value is ≤5 mgKOH / g; which can synergize with the diluent to enhance the compatibility and dispersibility of the system, and can avoid yellowing or decrease in aging resistance caused by migration of unreacted small molecules during the curing process, on the other hand, synergizes with the photosensitizer and the polyisocyanate to well balance the fluidity and curing rate of the system, and especially, the functional group of the vinyl ester resin is 2, and the acid value is ≤1 mgKOH / g, which can significantly improve the adhesive strength and hardness of the adhesive layer. The possible reason is that the adhesive layer composition is crosslinked by the diluent, and the active groups of the components react with each other to generate a three-dimensional network structure, thereby improving the adhesive strength and wear resistance and scratch resistance of the adhesive layer.

[0023] (3) The adhesive layer composition in the present application comprises the vinyl ester resin, the functional monomer, the photosensitizer, the diluent and the polyisocyanate, the components are simple, the curing speed is fast, the efficiency is high, and meanwhile, the problems of curing of the coating bottom layer and uncured surface can be avoided. In addition, the process does not need organic solvent, the pollution during the curing process is small, and the adhesive layer composition can be widely applied to the protection of the surfaces of glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen and metal plate. DETAILED DESCRIPTION

[0024] Example 1:

[0025] 1. A high-adhesion wear-resistant adhesive layer composition, the preparation raw materials of which comprise, by weight parts:

[0026] 14.5 parts of vinyl ester resin, 75 parts of functional monomer, 3.6 parts of photosensitizer, 18 parts of diluent, 4.2 parts of polyisocyanate;

[0027] The functional group of the vinyl ester resin is 2, and the acid value is ≤1 mgKOH / g (purchased from Guangzhou Lihou Trade Co., Ltd., model RJ311A80);

[0028] The functional monomer is 3-methyl-2-butene caffeic acid ester (CAS number: 118971-61-2);

[0029] The photosensitizer is a cationic photosensitizer and a free radical photosensitizer;

[0030] The weight ratio of the cationic photosensitizer to the free radical photosensitizer is 1:0.46;

[0031] The cationic photosensitizer is bis(4-dodecylphenyl) iodonium hexafluoroantimonate (CAS number: 71786-70-4);

[0032] The free radical photoinitiator is benzophenone;

[0033] The diluent is methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate;

[0034] The weight ratio of the methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate is 6.4:1:0.52:1.1;

[0035] The polyisocyanate is dicyclohexylmethane diisocyanate (CAS No.: 5124-30-1) and 1,6-hexane diisocyanate (CAS No.: 822-06-0);

[0036] The weight ratio of the dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate is 1:1-2;

[0037] 2. A preparation method of a high-adhesion wear-resistant adhesive layer composition:

[0038] The vinyl ester resin, functional monomer, photoinitiator, diluent, and polyisocyanate are weighed and mixed thoroughly to obtain the high-adhesion wear-resistant adhesive layer composition.

[0039] 3. Application of a high-adhesion wear-resistant adhesive layer composition, which can be applied to the protection of the surface of glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen, and metal plate.

[0040] Example 2:

[0041] 1. A high-adhesion wear-resistant adhesive layer composition, the preparation raw materials of which include, by weight:

[0042] 20 parts of vinyl ester resin, 85 parts of functional monomer, 5 parts of photoinitiator, 25 parts of diluent, and 6 parts of polyisocyanate.

[0043] The functional group of the vinyl ester resin is 2, and the acid value is ≤1 mgKOH / g;

[0044] The functional monomer is 3-methyl-2-butene caffeate;

[0045] The photoinitiator is a cationic photoinitiator and a free radical photoinitiator;

[0046] The weight ratio of the cationic photoinitiator to the free radical photoinitiator is 1:0.46;

[0047] The cationic photoinitiator is bis(4-dodecylphenyl) iodonium hexafluoroantimonate;

[0048] The free radical photoinitiator is benzophenone;

[0049] The diluent is methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate;

[0050] The weight ratio of the methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate is 6.4:1:0.52:1.1;

[0051] The polyisocyanate is dicyclohexylmethane diisocyanate and 1,6-hexane diisocyanate;

[0052] The weight ratio of the dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate is 1:1-2;

[0053] 2. A preparation method of a high-adhesion wear-resistant adhesive layer composition:

[0054] The vinyl ester resin, functional monomer, photosensitizer, diluent, and polyisocyanate are weighed and mixed thoroughly to obtain the high-adhesion wear-resistant adhesive layer composition.

[0055] 3. Application of a high-adhesion wear-resistant adhesive layer composition, which can be applied to the protection of the surface of glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen, and metal plate.

[0056] Comparative Example 1:

[0057] 1. A high-adhesion wear-resistant adhesive layer composition, the preparation raw materials of which include, by weight:

[0058] 14.5 parts of vinyl ester resin, 75 parts of functional monomer, 3.6 parts of photosensitizer, 18 parts of diluent, and 4.2 parts of polyisocyanate;

[0059] The functional group of the vinyl ester resin is 2, and the acid value is ≤5 mgKOH / g (purchased from Guangzhou Lihou Trade Co., Ltd., model RJ343);

[0060] The functional monomer is 3-methyl-2-butene caffeic acid ester;

[0061] The photosensitizer is a cationic photosensitizer and a free radical photosensitizer;

[0062] The weight ratio of the cationic photosensitizer to the free radical photosensitizer is 1:0.46;

[0063] The cationic photosensitizer is bis(4-dodecylphenyl) iodonium hexafluoroantimonate;

[0064] The free radical photosensitizer is benzophenone;

[0065] The diluent is methyl methacrylate, n-butyl acrylate, trimethylolpropane trimethyl acrylate, trimethylolpropane triacrylate;

[0066] The weight ratio of the methyl methacrylate, n-butyl acrylate, trimethylolpropane trimethyl acrylate, trimethylolpropane triacrylate is 6.4:1:0.52:1.1;

[0067] The polyisocyanate is dicyclohexylmethane diisocyanate and 1,6-hexane diisocyanate;

[0068] The weight ratio of the dicyclohexylmethane diisocyanate and 1,6-hexane diisocyanate is 1:1-2.

[0069] 2. A preparation method of a high-adhesion wear-resistant adhesive layer composition:

[0070] The vinyl ester resin, functional monomer, photosensitizer, diluent, and polyisocyanate are weighed and mixed thoroughly to obtain the high-adhesion wear-resistant adhesive layer composition.

[0071] 3. Application of a high-adhesion wear-resistant adhesive layer composition, which can be applied to the protection of the surface of glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen, and metal plate.

[0072] Comparative Example 2:

[0073] 1. A high-adhesion wear-resistant adhesive layer composition, the preparation raw materials of which include, by weight:

[0074] 14.5 parts of vinyl ester resin, 75 parts of functional monomer, 3.6 parts of photosensitizer, 18 parts of diluent, and 4.2 parts of polyisocyanate;

[0075] The functional group of the vinyl ester resin is 2, and the acid value is ≤1 mgKOH / g;

[0076] The functional monomer is 3-methyl-2-butene caffeate;

[0077] The photosensitizer is a cationic photosensitizer and a free radical photosensitizer;

[0078] The weight ratio of the cationic photosensitizer to the free radical photosensitizer is 1:0.46;

[0079] The cationic photosensitizer is bis(4-dodecylphenyl) iodonium hexafluoroantimonate;

[0080] The free radical photosensitizer is benzophenone;

[0081] The diluent is trimethylolpropane trimethyl acrylate, trimethylolpropane triacrylate, and n-butyl acrylate;

[0082] The weight ratio of the trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate is 1:0.52:1.1;

[0083] The polyisocyanate is dicyclohexylmethane diisocyanate and 1,6-hexane diisocyanate;

[0084] The weight ratio of the dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate is 1:1-2.

[0085] 2. A preparation method of a high-adhesion wear-resistant adhesive layer composition:

[0086] The vinyl ester resin, functional monomer, photosensitizer, diluent, and polyisocyanate are weighed and mixed thoroughly to obtain the composition.

[0087] 3. Application of a high-adhesion wear-resistant adhesive layer composition, which can be applied to the protection of the surface of glass, ceramic, chip, display screen, LED flexible circuit board, mobile phone screen, and metal plate.

[0088] Comparative Example 3:

[0089] 1. A high-adhesion wear-resistant adhesive layer composition, the preparation raw materials of which include, by weight:

[0090] 14.5 parts of a vinyl ester resin, 75 parts of a functional monomer, 3.6 parts of a photosensitizer, 18 parts of a diluent, and 4.2 parts of a polyisocyanate;

[0091] The functional group of the vinyl ester resin is 2, and the acid value is ≤1 mgKOH / g;

[0092] The functional monomer is 3-methyl-2-butene caffeate;

[0093] The photosensitizer is a cationic photosensitizer and a free radical photosensitizer;

[0094] The cationic photosensitizer

[0095] The weight ratio of the cationic photosensitizer to the free radical photosensitizer is 1:0.46;

[0096] The cationic photosensitizer is bis(4-dodecylphenyl) iodonium hexafluoroantimonate;

[0097] The free radical photosensitizer is benzophenone;

[0098] The diluent is methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and n-butyl acrylate;

[0099] The weight ratio of the methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, n-butyl acrylate is 6.4:1:0.52:1.1;

[0100] The polyisocyanate is dicyclohexylmethane diisocyanate.

[0101] 2. A method for preparing a high-adhesion wear-resistant adhesive layer composition:

[0102] The vinyl ester resin, functional monomer, photosensitizer, diluent, and polyisocyanate are weighed and mixed thoroughly to obtain the product.

[0103] 3. Use of a high-adhesion wear-resistant adhesive layer composition, which can be applied to the surface protection of glass, ceramic, chips, display screens, LED flexible circuit boards, mobile phone screens, and metal plates.

[0104] Performance test:

[0105] 1. Adhesion strength: The adhesive layer compositions prepared in Examples 1 and 2 and Comparative Examples 1-3 were applied to a plastic substrate at a thickness of 24 μm, and the test pieces were coated on polyethylene terephthalate (PET), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), and glass as the adherends by passing a 2 kg roller back and forth twice. The test pieces were cut to a width of 25 mm, and the 180° peel strength was measured after 1 hour of adhesion in an atmosphere of 23°C and 50% RH.

[0106] 2. Scratch and wear resistance: RCA test, 175 g, 500 times

[0107]

[0108]

Claims

1. A highly adhesive and wear-resistant adhesive layer composition, characterized in that, The raw materials for its preparation, by weight, include: 10-20 parts vinyl ester resin, 65-85 parts functional monomer, 1-5 parts photosensitizer, 15-25 parts diluent, 2-6 parts polyisocyanate; The vinyl ester resin has a functional group degree of 2 and an acid value ≤1mgKOH / g; The diluent is methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and n-butyl acrylate; the weight ratio of methyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and n-butyl acrylate is 4-8:1:0.3-0.7:0.8-1.

5. The polyisocyanate is dicyclohexylmethane diisocyanate or 1,6-hexanediisocyanate; the weight ratio of dicyclohexylmethane diisocyanate to 1,6-hexanediisocyanate is 1:1-2. The functional monomer is 3-methyl-2-buten-caffeic acid ester.

2. The highly adhesive and wear-resistant adhesive layer composition as described in claim 1, characterized in that, The photosensitizer is selected from at least one of cationic photosensitizers and free radical photosensitizers.

3. The highly adhesive and wear-resistant adhesive layer composition as described in claim 1 or 2, characterized in that, The photosensitizer is a cationic photosensitizer or a free radical photosensitizer.

4. The highly adhesive and wear-resistant adhesive layer composition as described in claim 3, characterized in that, The cationic photosensitizer is selected from at least one of diaryliodomonium salt, triaryliodomonium salt, alkyliodomonium salt, and cumeneferrocene hexafluorophosphate.

5. A method for preparing a highly adhesive and wear-resistant adhesive layer composition according to any one of claims 1-4, characterized in that, Weigh out the vinyl ester resin, functional monomer, photosensitizer, diluent, and polyisocyanate and mix thoroughly to obtain the final product.

6. The application of a highly adhesive and abrasion-resistant adhesive layer composition as described in any one of claims 1-4, characterized in that, It is used for the protection of glass, ceramics, chips, displays, LED flexible circuit boards, and metal plate surfaces.

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